Chaudhery Mustansar Hussain

Chaudhery Mustansar Hussain
Editor
Handbook of
Environmental
Materials
Management
Handbook of Environmental Materials
Management
Editor
Handbook of
Environmental Materials
Management
With 811 Figures and 417 Tables

Editor
Department of Chemistry and Environmental Science
New Jersey Institute of Technology
Newark, NJ, USA
ISBN 978-3-319-73644-0 ISBN 978-3-319-73645-7 (eBook)

ISBN 978-3-319-73646-4 (print and electronic bundle)
https://doi.org/10.1007/978-3-319-73645-7
Library of Congress Control Number: 2019933557
© Springer Nature Switzerland AG 2019

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I would like to dedicate
this handbook to
My beloved Holy Prophet (May the blessings
and the peace of Allah be upon him
(Muhammad))
“Mera Pyarey Aqa: App Sall Allāhu ʿAlay-Hi
Wa-Sallam”
Preface
Environmental management is the management of the interaction and impact of

human societies on the environment. It offers research and opinions on the use and
conservation of natural resources, protection of habitats, and control of hazards.
Modern environmental management of materials helps to minimize environmental
impacts by reducing the release of toxic substances to the environment and by
limiting human exposure. It also helps to reduce pressures on resources by
diminishing the quantities of materials that need to be extracted. Beyond this,
environmental management of materials supports sustainable decision-making by
balancing the social, environmental, and economic considerations throughout the
life cycle of a product or material, ensuring that negative impacts are not shifted from
the production process to the consumption phase, or vice versa. Modern environ-
mental management of materials therefore encourages the consideration of the
impacts of policies that affect a given target area, thereby promoting consideration
and possible identification of policy incoherence where this may be the case. Going
for green future and establishing a resource-efficient economy is therefore a major
environmental challenge today. In this context, putting in place policies that ensure
environmental materials management building on the principle of the 3Rs – Reduce,
Reuse, Recycle – is crucial. Environmental materials management can help both to
improve the environment, by reducing the amount of resources that human economic
activity requires as well as diminishing the associated environmental impacts, and to
improve resource security and competitiveness. However, till today, the advanced
comprehensive understanding and real-world applications of these environmental
materials management strategies are still at distance. This handbook summarizes
recent progresses and developments for modern environmental materials manage-
ment at both experimental and theoretical model scales.
To capture the comprehensive overview of the modern environmental materials
management and to offer reader a systematic and coherent pattern of the topic and
focused up-to-date reference, the handbook is divided into several parts, where each
Part comprises of several chapters, starting with introduction where modern inven-
tive perspective of environmental materials management is grasped. Part 1 discusses
major environmental issues and problems. Part 2 describes various site remediation
technologies that help to manage the modern environment. Parts 3, 4, and 5 elaborate
several waste management techniques for hazardous, radioactive, and special
vii
viii Preface
wastes. Part 6 is dedicated to environmental analysis, while Part 7 talks about various
environmental treatment technologies. Parts 8, 9, and 10 describe environmental
management of biomaterials, mathematical modeling, and management of
nanomaterial-based waste. Part 11 defines fate and transport of pollutants in the
environment.
Parts 12 and 13 explain environmental risk assessment and socioeconomic factors
for modern environmental materials management. The last Part clarifies the role of
pollution prevention in terms of sustainability and green world.
The future of modern environmental materials management is the last content to
summarize the book.
The aim of this book is to deliver the recent advancements in environmental
materials management techniques because of modern social demands. This hand-
book is intended for a very broad audience working in the fields of advanced
environmental management as a part of materials science, environment, green
chemistry, sustainability, environmental engineering, environmental sciences, etc.
This handbook will be an invaluable reference source for the libraries in universities
and industrial institutions, government and independent institutes, individual
research groups, and scientists working in the field of environment. Overall, this
handbook is planned to be useful for advanced undergraduate, graduate students,
researchers, and scientists who are searching for new and advanced technologies for
environmental materials management.
The editor and contributors are well-known researchers, scientists, and true pro-
fessionals from the academia and industry. On behalf of Springer, we are very
grateful to the authors of all chapters for their outstanding and passionate efforts in
the making of this handbook. Special thanks to Miss Anita Lekhwani (Senior
Editor), Miss Alexa Steele (Editor, Major Reference Works), Miss Aparajita Basu,
and the Springer Reference Editorial Team for their enthusiastic support and help
during this project. In the end, all thanks to Springer for publishing the handbook.
Chaudhery Mustansar Hussain, Ph.D.

The Editor
Contents
Volume 1
Part I Major Environmental Issues and Problems .............. 1
1 Assessment of Some Aspects of Provisioning Sewerage

Systems: A Case Study of Urban Agglomerations in Ganga
River Basin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Saurabh Shukla and Vinod Tare
2 Economic Assessment of Provisioning a Comprehensive Solid
Waste Management System: A Case Study of Urban
Agglomerations in Ganga River Basin . . . . . . . . . . . . . . . . . . . . . 35
Smriti Gupta, Saurabh Shukla, and Vinod Tare
3 Decentralized Integrated Approach of Water and Wastewater
Management in Rural West Bengal . . . . . . . . . . . . . . . . . . . . . . . 65
Pankaj Kumar Roy, Somnath Pal, Arunabha Majumder,
Gourab Banerjee, and Asis Mazumdar
4 Major Issues on Beneficial Utilization of Solar Energy
in India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Debanjan Sannigrahi
5 Major Environmental Issues and Problems of South Asia,
Particularly Bangladesh . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
G. N. Tanjina Hasnat, Md. Alamgir Kabir, and Md. Akhter Hossain
6 Air Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Saliha Saadet Kalender and Güler Bilen Alkan
7 Status of Particulate Matter Pollution in India: A Review . . . . . . 167
Geetanjali Kaushik, Arvind Chel, Satish Patil, and
Shivani Chaturvedi
8 Global Environmental Issues ............................ 195
Alsharifa Hind Mohammad
ix
x Contents
9 Fluoride Contamination in Groundwater and the Source

Mineral Releasing Fluoride in Groundwater of Indo-Gangetic
Alluvium, India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
Abhishek Saxena
10 Identification of the Source Mineral Releasing Arsenic in the

Groundwater of the Indo-Gangetic Plain, India . . . . . . . . . . . . . . 247
Pooja Goel
11 Industrial Solid Waste Management in a Developing Country

Governorate and the Opportunities for the Application of
Cleaner Production Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
Aida O. Al-Batnij, Issam A. Al-Khatib, and Stamatia Kontogianni
12 Indoor Air Pollution Around Industrial Areas and Its Effect:

A Case Study in Delhi City . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
Jitendra Kumar Nagar, Raj Kumar, J. P. Shrivastava, and
Geetanjali Kaushik
13 Scenario of Landfilling in India: Problems, Challenges, and

Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
Swati, Indu Shekhar Thakur, Virendra Kumar Vijay, and
Pooja Ghosh
14 Environmental Health Problems Due to Air Pollution

Exposure: A Case Study of Respiratory and Associated
Morbidities Among Traffic Police Personnel in Aurangabad
City of Maharashtra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Suchirai Gaikwad, N. N. Bandela, Geetanjali Kaushik, and
15 Microplastics as Contaminant in FreshWater Ecosystem:

A Modern Environmental Issue . . . . . . . . . . . . . . . . . . . . . . . . . . 355
Muafia Shafiq, Abdul Qadir, and Chaudhery Mustansar Hussain
16 Impact of Material Chemistry on the Performance

characteristics of a Coal Handling Plant . . . . . . . . . . . . . . . . . . . 379
Kumar Harshit, Syed Ali Hussain Jafri, and Pallav Gupta
Part II Environmental Site Remediation . . . . . . . . . . . . . . . . . . . . . 415
17 Technologies for Treatment of Colored Wastewater from

Different Industries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417
Shraddha Khamparia and Dipika Jaspal
Contents xi
18 Application of Novel Microbial Consortia for Environmental

Site Remediation and Hazardous Waste Management Toward
Low- and High-Density Polyethylene and Prioritizing the
Cost-Effective, Eco-friendly, and Sustainable Biotechnological
Intervention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
Sinosh Skariyachan, Meghna Manjunath, Apoorva Shankar,
Nikhil Bachappanavar, and Amulya A. Patil
19 Micro-remediation of Metals: A New Frontier in
Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
A. Banerjee, M. K. Jhariya, D. K. Yadav, and A. Raj
20 Biostimulation and Bioaugmentation: An Alternative Strategy
for Bioremediation of Ground Water Contaminated Mixed
Landfill Leachate and Sea Water in Low Income ASEAN
Countries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
Jubhar C. Mangimbulude and Ronald Kondo Lembang
21 Bacterial Cell-Mineral Interface, Its Impacts on Biofilm
Formation and Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
Hamid M. Pouran
22 Bioremediation of Mined Waste Land . . . . . . . . . . . . . . . . . . . . . 557
Nisha Rani, Hardeep Rai Sharma, Anubha Kaushik, and
Anand Sagar
23 Soil Pollution and Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
Nataša Stojić, Snežana Štrbac, and Dunja Prokić
Part III Hazardous Waste Management . . . . . . . . . . . . . . . . . . . . . . 617
24 Development of an Environmentally Sustainable Approach

for Safe Disposal of Arsenic-Rich Sludge . . . . . . . . . . . . . . . . . . . 619
Pankaj Kumar Roy, Arunabha Majumder, Somnath Pal,
Gourab Banerjee, Malabika Biswas Roy, Jayanta Debbarma, and
Asis Mazumdar
25 Household Hazardous Waste Quantification, Characterization,
and Management in Developing Countries’ Cities: A Case
Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635
Waseem M. W. Al-Tamimi, Issam A. Al-Khatib, and Stamatia
Kontogianni
26 Investigation of the Chemical Content of Two Specific Streams
in Municipal Waste: The Case of Hazardous Household Waste
and Dental Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657
Stamatia Kontogianni, Nicolas Moussiopoulos, and
Issam A. Al-Khatib
xii Contents
27 Management of Hazardous Paper Mill Wastes for Sustainable

Agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 679
A. K. Sannigrahi
28 Management of Municipal Solid Waste in Morocco: The Size

Effect in the Distribution of Combustible Components and
Evaluation of the Fuel Fractions . . . . . . . . . . . . . . . . . . . . . . . . . . 701
A. Ouigmane, Otmane Boudouch, Aziz Hasib, and M. Berkani
29 Hazardous Waste Management with Special Reference to

Biological Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
Soumya Nair and Jayanthi Abraham
Part IV Management of Radioactive Wastes . . . . . . . . . . . . . . . . . . 741
30 Management of Radioactive Wastes . . . . . . . . . . . . . . . . . . . . . . . 743

Bouchra El Hilal, Mohammed Hussein Rafeq Khudhair, and
Ahmed El Harfi
31 Actinide Speciation in Environment and Their Separation

Using Functionalized Nanomaterials and Nanocomposites . . . . . 771
N. Priyadarshini, K. Benadict Rakesh, and P. Ilaiyaraja
Part V Management of Special Wastes: CO2, CH4, NOX, SO2,

Carbon Particles, and Oil Spills . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 819
32 Prospects and Issues of Phosphorus Recovery as Struvite from

Waste Streams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 821
Sampriti Kataki and D. C. Baruah
33 Global Status of Nitrate Contamination in Groundwater:

Its Occurrence, Health Impacts, and Mitigation Measures . . . . . 869
Saurabh Shukla and Abhishek Saxena
34 Remediation of Industrial and Automobile Exhausts for

Environmental Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 889
Sukanchan Palit and Chaudhery Mustansar Hussain
35 Management of Residues from Air Pollution Control

Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 907
Christof Lanzerstorfer
Contents xiii
Volume 2
Part VI Environmental Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 927
36 Tailor-Made Molecular Traps for the Treatment of

Environmental Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 929
Rüstem Keçili, Özlem Biçen Ünlüer, and
37 Removal of Pharmaceutically Active Compounds from
Contaminated Water and Wastewater Using Biochar as
Low-Cost Adsorbents, An Overview . . . . . . . . . . . . . . . . . . . . . . . 951
Adel Al-Gheethi, Efaq Ali Noman, Radin Mohamed,
Mohd Adib Mohammad Razi, and M. K. Amir Hashim
38 Microbial Risk Associated with Application of Biosolids in
Agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 961
Abd. Halid Abdullah, and M. K. Amir Hashim
39 Monitoring and Risk Analysis of PAHs in the Environment . . . . 973
Karishma Hussain, Raza R. Hoque, Srinivasan Balachandran,
Subhash Medhi, Mohammad Ghaznavi Idris, Mirzanur Rahman, and
Farhaz Liaquat Hussain
40 Water Quality Assessment of an Unexplored Tropical
Freshwater System in Thiruvananthapuram, India:
A Multivariate Statistical Approach . . . . . . . . . . . . . . . . . . . . . . . 1009
Anila P. Ajayan, Jan W. Rijstenbil, and K. G. Ajit Kumar
41 Nanomembranes for Environment . . . . . . . . . . . . . . . . . . . . . . . . 1033
42 Exergy and Life Cycle-Based Analysis . . . . . . . . . . . . . . . . . . . . . 1057
Niloufar Salehi, Morteza Mahmoudi, Alireza Bazargan, and
Gordon McKay
43 Magnetic and Nanostructural Properties of Cobalt–Zinc
Ferrite for Environmental Sensors . . . . . . . . . . . . . . . . . . . . . . . . 1079
A.-H. El Foulani, R. C. Pullar, M. Amjoud, K. Ouzaouit, and
A. Aamouche
44 New Trends in Environmental Analysis . . . . . . . . . . . . . . . . . . . . 1097
Awad Ageel Al-rashdi
45 Integrated Evaluation of Quantitative Factors Related to the
Environmental Quality Scenario . . . . . . . . . . . . . . . . . . . . . . . . . . 1117
Gustavo Marques da Costa, Annette Droste, Darlan Daniel Alves,
and Daniela Montanari Migliavacca Osório
xiv Contents
46 Characterizing the Cell Surface Properties of

Hydrocarbon-Degrading Bacterial Strains, a Case Study . . . . . . 1139
Hamid M. Pouran, Steve A. Banwart, and Maria Romero-Gonzalez
47 Preparation, Characterization, and Heavy Metal Ion Adsorption

Property of APTES-Modified Kaolin: Comparative Study
with Original Clay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1167
Bahia Meroufel and Mohamed Amine Zenasni
48 Concept Note on Method Development for Speciation and

Measurement of Arsenic (As) in Its Valence States (As (III)
and As (V)) in Solid and Semisolid Organic Environmental
Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1191
A. M. M. Maruf Hossain
49 Determination of Select Heavy Metals in Air Samples from

Aurangabad City . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1199
Onkar Jogdand, N. N. Bandela, Geetanjali Kaushik, and Arvind Chel
50 Recent Advances in Membrane Extraction Techniques for

Environmental Samples Analysis . . . . . . . . . . . . . . . . . . . . . . . . . 1209
Hadi Tabani, Saeed Nojavan, Kamal Khodaei, and Alireza Bazargan
51 Environmental Toxicology and Air Pollution: A Comparative

Analysis of Different Methods and Studies . . . . . . . . . . . . . . . . . . 1243
Gustavo Marques da Costa, Larissa Meincke, Darlan Daniel Alves,
Ane Katiussa Siqueira Frohlich, Sandra Manoela Dias Macedo, and
Daniela Montanari Migliavacca Osório
52 The Effects of Atmospheric Pollution in Respiratory Health . . . . 1271

Sandra Magali Heberle, Gustavo Marques da Costa, Nelson Barros,
and Michele S. G. Rosa
Part VII Environmental Treatment Technologies . . . . . . . . . . . . . . 1287
53 Advanced Treatment Technologies . . . . . . . . . . . . . . . . . . . . . . . . 1289

Manviri Rani and Uma Shanker
54 Treatment of Domestic Gray Water by Multicomponent

Filters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1341
R. M. S. Radin Mohamed, Adel Al-Gheethi,
Muhammad Shabery Sainudin, and M. K. Amir Hashim
55 Development In-House: A Trap Method for Pretreatment of Fat,

Oil, and Grease in Kitchen Wastewater . . . . . . . . . . . . . . . . . . . . 1351
R. M. S. Radin Mohamed, Adel Al-Gheethi, A. N. Welfrad, and
M. K. Amir Hashim
Contents xv
56 Environmental Treatment Technologies: Adsorption . . . . . . . . . . 1367

Subramanyam Busetty
57 Making Artificial Beachrock Through Bio-cementation:

A Novel Technology to Inhibition of Coastal Erosion . . . . . . . . . . 1399
Md. Nakibul Hasan Khan and Satoru Kawasaki
58 Potential of Biogas Technology in Achieving the Sustainable

Developmental Goals: A Review Through Case Study in
Rural South Africa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1423
T. E. Rasimphi, D. Tinarwo, and W. M. Gitari
59 A Review on Treatment of Pharmaceuticals and Personal

Care Products (PPCPs) in Water and Wastewater . . . . . . . . . . . . 1433
Mukesh Goel and Ashutosh Das
60 Constructed Wetland: A Green Approach to Handle

Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1445
Ashutosh Das and Mukesh Goel
61 How to Improve Selectivity of a Material for Adsorptive

Separation Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1469
Vipin K. Saini and Aparajita Shankar
62 Advanced Pretreatment Strategies for Bioenergy Production

from Biomass and Biowaste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1507
C. Veluchamy, Ajay S. Kalamdhad, and Brandon H. Gilroyed
63 Green Infrastructure: Cost-Effective Nature-Based Solutions

for Safeguarding the Environment and Protecting Human
Health and Well-Being . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1525
Daniel Jato-Espino, Luis A. Sañudo-Fontaneda, and
Valerio C. Andrés-Valeri
64 The Modified Bardenpho Process . . . . . . . . . . . . . . . . . . . . . . . . . 1551

Ehsan Banayan Esfahani, Fatemeh Asadi Zeidabadi,
Alireza Bazargan, and Gordon McKay
65 Diagnostic and Treatment by Different Techniques of Leachates

from Municipal Solid Waste in Morocco Using Experimental
Design Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1593
Meriem Abouri, Salah Souabi, and M. Abdellah Bahlaoui
66 Application of Liquid Chromatography-Mass Spectrometry for

the Analysis of Endocrine Disrupting Chemical Transformation
Products in Advanced Oxidation Processes and Their Reaction
Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1633
Jin-Chung Sin, Sze-Mun Lam, and Abdul Rahman Mohamed
xvi Contents
67 Olive Mill Wastewater: Treatment and Valorization

Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1659
Yahia Rharrabti and Mohamed EI Yamani
68 Studies on Water Quality of Mokokchung District, Nagaland,
India, and Removal of Trace Elements Using Activated Carbon
Prepared from Locally Available Bio-waste . . . . . . . . . . . . . . . . . 1687
Daniel Kibami
69 Advancement of Photocatalytic Water Treatment Technology
for Environmental Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1719
Sze-Mun Lam, Jin-Chung Sin, and Abdul Rahman Mohamed
70 Techniques for Remediation of Paper and Pulp Mill Effluents:
Processes and Constraints . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1747
Smita Chaudhry and Rashmi Paliwal
71 Biofilm-Based Systems for Industrial Wastewater Treatment . . . 1767
Meryem Asri, Soumya Elabed, Saad Ibnsouda Koraichi, and
Naïma El Ghachtouli
72 Role of Bioremediation as a Low-Cost Adsorbent for
Excessive Fluoride Removal in Groundwater . . . . . . . . . . . . . . . . 1789
Abhishek Saxena and Anju Patel
73 Biotechnological Approach for Mitigation Studies of Effluents
of Automobile Industries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1821
N. N. Bandela, P. N. Puniya, and Geetanjali Kaushik
74 New Techniques for Treatment and Recovery of Valuable
Products from Olive Mill Wastewater . . . . . . . . . . . . . . . . . . . . . 1839
Reda Elkacmi and Mounir Bennajah
75 Role of Earthworms in Managing Soil Contamination . . . . . . . . 1859
Payal Garg, Geetanjali Kaushik, Jitendra Kumar Nagar, and
Poonam Singhal
76 The Application of Membrane Bioreactors (MBR) for the
Removal of Organic Matter, Nutrients, and Heavy Metals from
Landfill Leachate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1879
Susan Hayeri Yazdi, Ali Vosoogh, and Alireza Bazargan
Volume 3
Part VIII Environmental Management of Biomaterials ......... 1899
77 Sustainable Biomedical Waste Management . . . . . . . . . . . . . . . . 1901

Contents xvii
78 Agrowaste Materials as Composites for Biomedical

Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1925
Geetanjali Kaushik, Poonam Singhal, and Arvind Chel
Part IX Environmental Modeling (Mathematical Modeling

and Environmental Problems) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1941
79 A New Method to Estimate the Instantaneous NOx Emissions

from Road Traffic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1943
Hicham Gourgue
80 Water Balance Models in Environmental Modeling . . . . . . . . . . . 1961
Khodayar Abdollahi, Alireza Bazargan, and Gordon McKay
81 Modeling the Feasibility of Employing Solar Energy for Water
Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1977
Hisham A. Maddah
82 Applications of Soft Computing Methods in Environmental
Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2001
Kaan Yetilmezsoy
83 Modelization of Trihalomethanes Formation in Drinking Water
Distribution Systems in France . . . . . . . . . . . . . . . . . . . . . . . . . . . 2047
Otmane Boudouch, C. Galey, C. Rosin, and A. Zeghnoun
Part X Environmental Nanotechnology: Management of

Nano-waste (Nanomaterials) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2061
84 Nano-wastes and the Environment: Potential Challenges and

Opportunities of Nano-waste Management Paradigm for
Greener Nanotechnologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2063
Sherif A. Younis, Esraa M. El-Fawal, and Philippe Serp
85 Homeopathic Nanomedicines and Their Effect on the
Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2135
P. Nandy, P. Bandyopadhyay, M. Chakraborty, A. Dey, D. Bera,
B. K. Paul, S. Kar, A. Gayen, R. Basu, S. Das, D. S. Bhar, S. Manna,
R. K. Manchanda, A. K. Khurana, and D. Nayak
86 Environmental Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . 2159
Junaid Saleem, Usman Bin Shahid, and Gordon McKay
87 Engineered Nanomaterials in the Environment, Their
Potential Fate and Behavior and Emerging Techniques
to Measure Them . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2191
Hamid M. Pouran
xviii Contents
88 Environmental Nanotechnology and Education for Sustainability:

Recent Progress and Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . 2205
Abdelaziz El Moussaouy
89 Nanotechnology Interaction with Environment . . . . . . . . . . . . . . 2233

Rigers Bakiu
90 Nanowaste Classification, Management, and Legislative

Framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2257
Rigers Bakiu
91 Current Status and Perspectives in Nanowaste Management . . . 2287

Astrid Campos and Israel López
Part XI Fate and Transport of Pollutants-LCA ................ 2315
92 Transport and Fate of Mercury (Hg) in the Environment:

Need for Continuous Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . 2317
Zia Mahmood Siddiqi
93 Life-Cycle Assessment of Construction Materials: Analysis of

Environmental Impacts and Recommendations of Eco-efficient
Management Practices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2337
Leonor Patricia Güereca, Daniel Jato-Espino, and
Esther Lizasoain-Arteaga
94 Dispersion, Photochemical Transformation, and Bioaccumulation

of Pollutants in the Vicinity of Highway . . . . . . . . . . . . . . . . . . . . 2373
Gennady Gerasimov
Part XII Environmental Risk Assessment . . . . . . . . . . . . . . . . . . . . . 2395
95 Metabolic Toxicity and Alteration of Cellular Bioenergetics by

Hexavalent Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2397
Sudipta Pal and Kanu Shil
96 Recent Advances in Toxicology of Gold Nanoparticles . . . . . . . . 2425

Siva Prasad Bitragunta, S. Aarathi Menon, and P. Sankar Ganesh
97 Performance Evaluation of Global Environmental Impact

Assessment Methods Through a Comparative Analysis of
Legislative and Regulatory Provisions . . . . . . . . . . . . . . . . . . . . . 2441
Lekha Sridhar and Vaibhav Gupta
98 Environmental Impact of Steel Industry . . . . . . . . . . . . . . . . . . . 2463

Andrea Di Schino
Contents xix
99 Spatial Variation in the Grain Size Characteristics of Sediments

in Ramganga River, Ganga Basin, India . . . . . . . . . . . . . . . . . . . 2485
Mohd Yawar Ali Khan
100 Integrated Assessment of Environmental Factors: Risks to

Human Health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2497
Gustavo Marques da Costa and Michele dos Santos Gomes da Rosa
Volume 4
Part XIII Environmental Policy, Laws, and Economics . . . . . . . . . . 2513
101 Implications of International Environmental Laws: A Close

Enquiry at the International Levels to Protect the
Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2515
Noor Mohammad
102 The Role of Local Government Laws in Bangladesh for

Promoting Environmental Justice in the Union Parishads of
Bangladesh: A Case Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2537
Noor Mohammad
103 Research Prioritization in Aerosol Geo-Engineering . . . . . . . . . . 2559

104 Environmental Law and Policy in the Russian Federation:

An Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2569
Ekaterina A. Belokrylova
105 Critical Assessment of Existing Environmental Legislation and

Policies in India, Its Benefits, Limitation, and Enforcement . . . . 2591
Anirban Dhulia and Rajiv Ganguly
Part XIV Pollution Prevention, Sustainability, and Green

World . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2603
106 A Safety Promotion Approach for Handling of Chemicals in

the Working Environmental Management . . . . . . . . . . . . . . . . . . 2605
A. Umamaheswari, S. Lakshmana Prabu, M. Rengasamy, and
G. Venkatesan
107 The Importance and Potential of Duckweeds as a Model and

Crop Plant for Biomass-Based Applications and Beyond . . . . . . 2629
Hieu X. Cao, Paul Fourounjian, and Wenqin Wang
xx Contents
108 Enhancing Resilience of Vulnerable Coastal Areas and

Communities: Mangrove Rehabilitation/Restoration Works
in the Gambia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2647
Jean-Hude E. Moudingo, Gordon Ajonina, Diyouke M. Eugene,
Ansumana K. Jarju, Kwasu Jammeh, Foday Conteh, Saul Taal,
Lamin Mai Touray, Modou Njei, and Saiko Janko
109 Assessment of the Biogas Potential in the Vhembe District of
Limpopo: A Case Study of Waste-to-Energy Conversion
Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2693
110 Biosynthesis and Assemblage of Extracellular Cellulose by
Bacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2703
Sumathi Suresh
111 Wastewater Management to Environmental Materials
Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2745
Musarrat Parween and A. L. Ramanathan
112 The Evolution of the Paradigm of Pollution Prevention and
Sustainability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2769
W. I. Jose
113 Bioremediation of Hormones from Waste Water . . . . . . . . . . . . . 2801
Anushree Suresh and Jayanthi Abraham
114 An Introduction to Sustainable Materials Management . . . . . . . . 2831
Mohaddeseh Khorasanizadeh, Alireza Bazargan, and
Gordon McKay
115 Air Pollution Prevention Technologies . . . . . . . . . . . . . . . . . . . . . 2871
Saliha Saadet Kalender
116 Camelina sativa: An Emerging Biofuel Crop . . . . . . . . . . . . . . . . 2889
Shivani Chaturvedi, Amrik Bhattacharya, Sunil Kumar Khare, and
Geetanjali Kaushik
117 Sustainability of Waste Glass Powder and Clay Brick Powder
as Cement Substitute in Green Concrete . . . . . . . . . . . . . . . . . . . 2927
O. M. Olofinnade, A. N. Ede, and C. A. Booth
118 Dynamic Agro-economic Modeling for Sustainable Water
Resources Management in Arid and Semi-arid Areas . . . . . . . . . 2949
Hayat Lionboui, Tarik Benabdelouahab, Aziz Hasib, Fouad Elame,
and Abdelali Boulli
119 Photovoltaic Systems and Equipments for the Rural and
Urban World . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2975
Mustapha Melhaoui, Kamal Hirech, Ilias Atmane, and Khalil Kassmi
Contents xxi
120 Seed Germination and Propagation for Regeneration of Some

Medicinal Plants Growing Wild in Semiarid Region of
Algeria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3007
Souad Mehalaine
121 Impact of Climate Change and Land Use Change Scenarios on
Water Resources in Tha Chin River Basin: A Case Study of
Suphan Buri Province, Thailand . . . . . . . . . . . . . . . . . . . . . . . . . 3031
Sathaporn Monprapussorn
122 An Evaluation of Usage of Methyl Esters of Jatropha and Fish
Oil for Environmental Protection . . . . . . . . . . . . . . . . . . . . . . . . . 3041
S. Sendilvelan and K. Bhaskar
123 Modern Environmental Materials, Pollution Prevention,
Sustainability, and Green World . . . . . . . . . . . . . . . . . . . . . . . . . . 3069
Mohammed Hussein Rafeq Khudhair, Bouchra El Hilal,
M. S. Elyoubi, and Ahmed Elharfi
124 Stabilization of Black Cotton Soil Using Waste Glass . . . . . . . . . 3099
Niraj Singh Parihar, Vijay Kumar Garlapati, and Rajiv Ganguly
125 Air Quality Status and Management in Tier II and III Indian
Cities: A Case Study of Aurangabad City, Maharashtra . . . . . . . 3115
Geetanjali Kaushik, Satish Patil, and Arvind Chel
126 Modern Air Pollution Prevention Strategies in the Urban
Environment: A Case Study of Delhi City . . . . . . . . . . . . . . . . . . 3137
Richa Dave Nagar and Geetanjali Kaushik
127 Environmental Management and Sustainable Development:
A Vision for the Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3163
128 Modern Social Media in Environmental Management and
Sustainability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3181
Poonam Singhal, Indranil Bose, Geetanjali Kaushik, and
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3203
About the Editor
Dr. Chaudhery Mustansar Hussain (born in 1975, in

Pakistan, has lived in the USA from 2009, and natural-
ized in the USA recently) is currently an Adjunct Pro-
fessor, an Academic Advisor, and Director of
Laboratories in the Department of Chemistry and Envi-
ronmental Science at the New Jersey Institute of Tech-
nology (NJIT), Newark, New Jersey, USA. Dr. Hussain
is an experienced Environmental Consultant who
worked for several projects sponsored by the Asian
Development Bank. Dr. Hussain completed his Ph.D.
in International Program in Environmental Management
from Chulalongkorn University, Bangkok, Thailand. He
is truly an educator with several years of experiences
and has privileged to present the knowledge, awareness,
and familiarity of environmental management from
industry to higher education research. His editorial
experience includes Editor of the Journal of Chemistry
(Hindawi Publishing), Guest Editor of ASME Journal
of Nanotechnology in Engineering and Medicine, Editor
of BAOJ Chemistry, and many more. Dr. Hussain is the
Author of numerous papers in peer-reviewed interna-
tional journals as well as prolific Author and Editor of
several scientific monographs and handbooks published
with Springer, Elsevier, the Royal Society of Chemistry,
John Wiley & Sons, CRC Press, etc. To date, he has
authored/edited more than 20 books and handbooks and
contributed toward more than 35 book chapters. His
research interests include environmental management,
environmental analysis, analytical chemistry, environ-
mental engineering, application of nanotechnology and
advanced materials for various industries, etc.
Dr. Hussain can speak several languages including
English, Urdu, Punjabi, and Thai.
xxiii
Contributors
A. Aamouche Applied Sciences National School (ENSA), Cadi Ayyad University,

Marrakech, Morocco
S. Aarathi Menon Department of Biological Sciences, BITS Pilani, Hyderabad
Campus, Hyderabad, Telangana, India
Khodayar Abdollahi Department of Engineering Measures for Nature Develop-
ment, Faculty of Natural Resources and Earth Sciences, Shahrekord University,
Shahrekord City, Iran
Abd. Halid Abdullah Micro-pollution Research Centre (MPRC), Department of
Water and Environmental Engineering, Faculty of Civil and Environmental
Engineering, Universiti Tun Hussein Onn Malaysia, Batu, Pahat, Malaysia
Meriem Abouri Laboratory of Process Engineering and Environment, Faculty of
Sciences and Techniques, Mohammedia, University – Hassan II, Mohammedia,
Morocco
Jayanthi Abraham Microbial Biotechnology Laboratory, School of Biosciences
and Technology, VIT University, Vellore, Tamil Nadu, India
Anila P. Ajayan Environmental Biology Division, Department of Botany,
Mahatma Gandhi College, University of Kerala, Thiruvananthapuram, Kerala, India
K. G. Ajit Kumar Kerala State Biodiversity Board, Thiruvananthapuram, Kerala,
India
Gordon Ajonina Cameroon Wildlife Conservation Society (CWCS), CWCS
Coastal, Forests and Mangrove Programme, Mouanko, Littoral Region, Cameroon
Aida O. Al-Batnij Faculty of Graduate Studies, Birzeit University, Birzeit,
Palestine
Adel Al-Gheethi Micro-Pollutant Research Centre (MPRC), Department of Water
and Environment Engineering, Faculty of Civil and Environmental Engineering,
University Tun Hussein Onn Malaysia (UTHM), Parit Raja, Johor, Malaysia
xxv
xxvi Contributors
Güler Bilen Alkan Barbaros Hayrettin Naval Architecture and Maritime Faculty,
Iskenderun Technical University, Hatay, Iskenderun, Turkey
Issam A. Al-Khatib Institute of Environmental and Water Studies, Birzeit
University, Birzeit, West Bank, Palestine
Awad Ageel Al-rashdi Department of Chemistry, Center for Scientific Research
(QCSR), Al-Qunfudah University College, Umm Al-Qura University, Makkah
Al-Mukarramah, Al-Qunfudah, Saudi Arabia
Waseem M. W. Al-Tamimi Faculty of Graduate Studies, Birzeit University,
Birzeit, West Bank, Palestine
Faculty of Graduate Studies, Birzeit University, Hebron, Palestine
Darlan Daniel Alves Programa de pós-graduação em Qualidade Ambiental,
Universidade Feevale, Novo Hamburgo, RS, Brazil
M. K. Amir Hashim Micro-Pollutant Research Centre (MPRC), Department of
Water and Environment Engineering, Faculty of Civil and Environmental Engineer-
ing, University Tun Hussein Onn Malaysia (UTHM), Parit Raja, Johor, Malaysia
M. Amjoud Laboratory of Condensed Matter and Nanostructures, Faculty of
Science and Technology, Cadi Ayyad University, Marrakech, Morocco
Valerio C. Andrés-Valeri GITECO Research Group, University of Cantabria,
Santander, Cantabria, Spain
Fatemeh Asadi Zeidabadi Department of Chemical and Petroleum Engineering,
Sharif University of Technology, Tehran, Iran
Meryem Asri Laboratoire de Biotechnologie Microbienne, Faculté des Sciences et
Techniques, Université Sidi Mohamed Ben Abdellah, Fes, Morocco
Ilias Atmane Faculty of Science, Department of Physics, Team: Materials,
Electronics and Renewable Energies MERE, Laboratory Electromagnetism Signal
Processing and Renewable Energy LESPRE, Mohamed Premier University, Oujda,
Morocco
Nikhil Bachappanavar R & D Centre, Department of Biotechnology Engineering,
Dayananda Sagar Institutions, Bengaluru, India
Visvesvaraya Technological University, Belagavi, Karnataka, India
Dayananda Sagar Institutions, Bengaluru, Karnataka, India
M. Abdellah Bahlaoui Laboratory of Materials, Catalysis and Development of
Natural Resources, Faculty of Sciences and Techniques, Mohammedia, University –
Hassan II, Mohammedia, Morocco
Rigers Bakiu Faculty of Agriculture and Environment, Agricultural University of
Tirana, Tirana, Albania
Contributors xxvii
Srinivasan Balachandran Department of Environmental Studies, Visva-

BharatiSantiniketan, Santiniketan, West Bengal, India
Ehsan Banayan Esfahani Department of Chemical and Petroleum Engineering,
Sharif University of Technology, Tehran, Iran
N. N. Bandela Department of Environmental Sciences, Dr. Babasaheb Ambedkar
Marathwada University, Aurangabad, Maharashtra, India
P. Bandyopadhyay Centre for Interdisciplinary Research and Education, Kolkata,
India
A. Banerjee Department of Environmental Science, Sarguja University,
Ambikapur, Chattisgarh, India
Gourab Banerjee School of Water Resources Engineering, Jadavpur University,
Kolkata, West Bengal, India
Steve A. Banwart School of Earth and Environment, University of Leeds, Leeds,
UK
Nelson Barros Energy, Environment and Health Research Unit, FP-ENAS - UFP:
University Fernando Pessoa, Porto, Portugal
D. C. Baruah Energy Conservation Laboratory, Department of Energy, Tezpur
University, Tezpur, Assam, India
Department of Mechanical and Industrial Engineering, University of South Africa,
Pretoria, South Africa
R. Basu Centre for Interdisciplinary Research and Education, Kolkata, India
Alireza Bazargan Department of Civil Engineering, K. N. Toosi University of
Technology, Tehran, Iran
Ekaterina A. Belokrylova Environmental Law and Policy Department, Science of
Institute of Law, The Udmurt State University, Izhevsk, Russia
Tarik Benabdelouahab National Institute of Agricultural Research, Research
Center of Tadla, Tadla, Morocco
K. Benadict Rakesh Department of Physics, Indian Institute of Technology
Madras, Chennai, Tamil Nadu, India
Mounir Bennajah Department of Process Engineering, National School of
Mineral Industries of Rabat, BP, Rabat, Morocco
D. Bera Centre for Interdisciplinary Research and Education, Kolkata, India
M. Berkani Laboratory of Spectro-Chemistry Applied and Environment, Univer-
sity Sultan MoulaySlimane, BeniMellal, Morocco
D. S. Bhar Centre for Interdisciplinary Research and Education, Kolkata, India
xxviii Contributors
K. Bhaskar Department Automobile Engineering, Rajalakshmi Engineering

College, Chennai, India
Amrik Bhattacharya Department of Chemistry, Indian Institute of Technology,
Delhi, India
Özlem Biçen Ünlüer Faculty of Science, Department of Chemistry, Anadolu
University, Eskişehir, Turkey
Siva Prasad Bitragunta Department of Biological Sciences, BITS Pilani,
Hyderabad Campus, Hyderabad, Telangana, India
Biotechnology Division, Environment Protection Training and Research Institute,
Hyderabad, Telangana, India
C. A. Booth University of the West of England, Bristol, UK
Indranil Bose Indian Institute of Management, Calcutta, India
Otmane Boudouch Transdisciplinary Team of Analytical Sciences for Sustainable
Development, University Sultan MoulaySlimane, BeniMellal, Morocco
Environmental and Agro-Industries Processes Team, University Sultan Moulay
Slimane, Beni Mellal, Morocco
Abdelali Boulli Laboratory of Environment and Valorization of Agro-Resources,
Sultan Moulay Slimane University, Beni Mellal, Morocco
Subramanyam Busetty SASTRA Deemed University, Thanjavur, India
Astrid Campos Universidad Autónoma de Nuevo León, UANL, Facultad de
Ciencias Químicas, Laboratorio de Materiales I, San Nicolás de los Garza, Nuevo
León, Mexico
Hieu X. Cao Institute of Biology/Plant Physiology, Martin-Luther-University of
Halle-Wittenberg, Halle, Saale, Germany
M. Chakraborty Centre for Interdisciplinary Research and Education, Kolkata,
India
Shivani Chaturvedi Department of Chemistry, Indian Institute of Technology
Delhi, New Delhi, India
Smita Chaudhry Institute of Environmental Studies, Kurukshetra University,
Kurukshetra, India
Arvind Chel MGM’s Jawaharlal Nehru Engineering College, Mahatma Gandhi
Mission, Aurangabad, Maharashtra, India
Foday Conteh Department of Water Resources, Abuko, Gambia
Gustavo Marques da Costa Programa de pós-graduação em Qualidade
Ambiental, Universidade Feevale, Novo Hamburgo, RS, Brazil
Universidade Feevale, Novo Hamburgo, Brazil
Contributors xxix
Michele dos Santos Gomes da Rosa Pontifícia Universidade Católica do Rio

Grande do Sul – PUCRS, Porto Alegre, Brazil
Ashutosh Das Centre for Environmental Engg., PRIST Deemed University,
Thanjavur, Tamil Nadu, India
S. Das Centre for Interdisciplinary Research and Education, Kolkata, India
Jayanta Debbarma PWD (Water Resources), Agartala, Tripura, India
A. Dey Centre for Interdisciplinary Research and Education, Kolkata, India
Anirban Dhulia Department of Civil Engineering, Jaypee University of Informa-
tion Technology, Himachal Pradesh, Waknaghat, India
Andrea Di Schino Dipartimento di Ingegneria, Università di Perugia, Perugia, Italy
Annette Droste Programa de pós-graduação em Qualidade Ambiental,
Universidade Feevale, Novo Hamburgo, RS, Brazil
A. N. Ede Covenant University, Ota, Ogun State, Nigeria
Mohamed EI Yamani Polydisciplinary Faculty of Taza, Taza, Morocco
Naïma El Ghachtouli Laboratoire de Biotechnologie Microbienne, Faculté des
Sciences et Techniques, Université Sidi Mohamed Ben Abdellah, Fes, Morocco
Ahmed El Harfi Laboratory of Agro resources Polymers and Process engineering
(LAPPE), Team of Macromolecular and Organic Chemistry, Faculty of sciences, Ibn
Tofail University, Kenitra, Morocco
Bouchra El Hilal Laboratory of Agro resources Polymers and Process engineering
Operation Unit of the Radioactive Waste, Center of Nuclear Studies of Maamora
(CENM) (CNESTEN), Kenitra, Morocco
Abdelaziz El Moussaouy Laboratory of Dynamics and Optics of Materials,
Department of Physics, Faculty of Sciences, Mohammed University; CRMEF-O,
Oujda, Morocco
Soumya Elabed Laboratoire de Biotechnologie Microbienne, Faculté des Sciences
et Techniques, Université Sidi Mohamed Ben Abdellah, Fes, Morocco
Fouad Elame National Institute of Agricultural Research, Research Center of
Agadir, Agadir, Morocco
Esraa M. El-Fawal Analysis and Evaluation Department, Egyptian Petroleum
Research Institute, Nasr City, Cairo, Egypt
Ahmed Elharfi Laboratory of Agro Resources Polymers and Process engineering
xxx Contributors
Reda Elkacmi Department of Chemistry and Valorisation, Faculty of Sciences

Ain-Chock, HASSAN II University of Casablanca, BP, Casablanca, Morocco
Department of Process Engineering, National School of Mineral Industries of Rabat,
BP, Rabat, Morocco
M. S. Elyoubi Laboratory of Chemistry of Solid State, Faculty of Science, Ibn
Diyouke M. Eugene Cameroon Wildlife Conservation Society (CWCS), CWCS
Coastal, Forests and Mangrove Programme, Mouanko, Littoral Region, Cameroon
A.-H. El Foulani MSISM Research Team, Department of Physics, Polydisciplinary
Faculty of Safi, Cadi Ayyad University, Safi, Morocco
Paul Fourounjian Waksman Institute of Microbiology, Rutgers University,
Piscataway, NJ, USA
Ane Katiussa Siqueira Frohlich UFMG, Belo Horizonte, Brazil
Suchirai Gaikwad Department of Environmental Sciences, Dr. Babasaheb
Ambedkar Marathwada University, Aurangabad, Maharashtra, India
C. Galey Agence nationale de santé publique 12 rue du Val d’Osne 94415, Saint
Maurice Cedex, France
Rajiv Ganguly Department of Civil Engineering, Jaypee University of Information
Technology, Waknaghat, Himachal Pradesh, India
Payal Garg Centre for Rural Development and Technology, Indian Institute of
Technology Delhi, New Delhi, India
Vijay Kumar Garlapati Department of Biotechnology and Bioinformatics, Jaypee
University of Information Technology, Waknaghat, Himachal Pradesh, India
A. Gayen Centre for Interdisciplinary Research and Education, Kolkata, India
Gennady Gerasimov Institute of Mechanics, Moscow State University, Moscow,
Russia
Pooja Ghosh Centre for Rural Development and Technology, Indian Institute of
Technology, New Delhi, India
Brandon H. Gilroyed School of Environmental Science, University of Guelph
Ridgetown Campus, Ridgetown, ON, Canada
W. M. Gitari Department of Ecology and Resource Management, University of
Venda, Thohoyandou, South Africa
Mukesh Goel Centre for Environmental Engg., PRIST Deemed University,
Thanjavur, Tamil Nadu, India
Pooja Goel Centre for Advanced Study in Geology, University of Lucknow,
Lucknow, India
Contributors xxxi
Hicham Gourgue Sustainable Innovation and Applied Research Laboratory

(SIARL) Universiapolis, International University of Agadir, Agadir, Morocco
Leonor Patricia Güereca Instituto de Ingeniería, Universidad Nacional Autónoma
de México, Coyoacán, Ciudad Universitaria, Mexico City, Mexico
Pallav Gupta Department of Mechanical Engineering, A.S.E.T., Amity University,
Noida, Uttar Pradesh, India
Smriti Gupta Faculty of Civil Engineering, Shri Ramswaroop Memorial
University, Lucknow, India
Vaibhav Gupta Council on Energy, Environment and Water (CEEW), New Delhi,
India
Kumar Harshit Department of Mechanical Engineering, A.S.E.T., Amity
University, Noida, Uttar Pradesh, India
Aziz Hasib Laboratory of Environment and Valorization of Agro-Resources,
Sultan Moulay Slimane University, Beni Mellal, Morocco
G. N. Tanjina Hasnat Department of Land Administration, Faculty of Land
Management and Administration, Patuakhali Science and Technology University,
Dumki, Patuakhali, Bangladesh
Susan Hayeri Yazdi Gas Turbine Power Plant Division, Monenco Iran Company,
Tehran, Iran
Sandra Magali Heberle Energy, Environment and Health Research Unit,
FP-ENAS - UFP: University Fernando Pessoa, Porto, Portugal
Kamal Hirech Faculty of Science, Department of Physics, Team: Materials,
Morocco
Raza R. Hoque Department of Environmental Science, Tezpur University, Tezpur,
Assam, India
Md. Akhter Hossain Institute of Forestry and Environmental Sciences Chittagong
University, University of Chittagong, Chittagong, Bangladesh
A. M. M. Maruf Hossain School of Global, Urban and Social Studies, College of
Design and Social Context, RMIT University, Melbourne, VIC, Australia
Center for Integrated Knowledge Invention, Laverton, VIC, Australia
Chaudhery Mustansar Hussain Department of Chemistry and Environmental
Sciences, New Jersey Institute of Technology, Newark, NJ, USA
Karishma Hussain Department of Bioengineering and Technology, Gauhati
University, Guwahati, Assam, India
xxxii Contributors
Farhaz Liaquat Hussain Research Scholar, Department of Chemistry, Dibrugarh

University, Dibrugarh, Assam, India
Saad Ibnsouda Koraichi Laboratoire de Biotechnologie Microbienne, Faculté des
Sciences et Techniques, Université Sidi Mohamed Ben Abdellah, Fes, Morocco
Centre Universitaire Régional d’Interface, Université Sidi Mohamed Ben Abdellah,
Fes, Morocco
Mohammad Ghaznavi Idris Department of Bioengineering and Technology
(GUIST), Gauhati University, Guwahati, India
P. Ilaiyaraja Department of Physics, Indian Institute of Technology Madras,
Chennai, Tamil Nadu, India
Syed Ali Hussain Jafri Department of Mechanical Engineering, Integral
University, Lucknow, Uttar Pradesh, India
Kwasu Jammeh Department of Parks and Wildlife Management, Kanifing,
Gambia
Saiko Janko KOMFORA, The Kombo/Foni Forestry Association, Kafuta, Gambia
Ansumana K. Jarju NARI, Brikama, West Coast Region, Gambia
Dipika Jaspal Symbiosis Institute of Technology, Symbiosis International
(Deemed University), Lavale, Pune, India
Daniel Jato-Espino GITECO Research Group, University of Cantabria, Santander,
Cantabria, Spain
M. K. Jhariya Department of Farm Forestry, Sarguja University, Ambikapur,
Chhattisgarh, India
Onkar Jogdand Department of Environmental Sciences, Dr. Babasaheb
Ambedkar Marathwada University, Aurangabad, Maharashtra, India
W. I. Jose Department of Chemical Engineering, University of the Philippines,
Quezon City, Metro Manila, Philippines
Md. Alamgir Kabir Department of Agroforestry, Patuakhali Science and
Technology University, Dumki, Patuakhali, Bangladesh
Ajay S. Kalamdhad Department of Civil Engineering, Indian Institute of
Technology Guwahati, Guwahati, India
Saliha Saadet Kalender Istanbul Technical University, Tirana, Albania
S. Kar Centre for Interdisciplinary Research and Education, Kolkata, India
Khalil Kassmi Faculty of Science, Department of Physics, Team: Materials,
Morocco
Contributors xxxiii
Sampriti Kataki Energy Conservation Laboratory, Department of Energy, Tezpur

University, Tezpur, Assam, India
Anubha Kaushik University School of Environment Management, Guru Gobind
Singh Indraprastha University, Dwarika, New Delhi, India
Geetanjali Kaushik MGM’s Jawaharlal Nehru Engineering College, Mahatma
Gandhi Mission, Aurangabad, Maharashtra, India
Satoru Kawasaki Faculty of Engineering, Hokkaido University, Sapporo, Japan
Rüstem Keçili Yunus Emre Vocational School of Health Services, Department of
Medical Services and Techniques, Anadolu University, Eskişehir, Turkey
Shraddha Khamparia Symbiosis Centre for Research and Innovation, Symbiosis
International (Deemed University), Lavale, Pune, India
Md. Nakibul Hasan Khan Department of Environmental Science and Engineer-
ing, Jatiya Kabi Kazi Nazrul Islam University, Mymensingh, Bangladesh
Mohd Yawar Ali Khan Department of Earth Sciences, Indian Institute of Tech-
nology Roorkee, Roorkee, India
Sunil Kumar Khare Department of Chemistry, Indian Institute of Technology,
New Delhi, India
Kamal Khodaei Department of Environmental Geology, Research Institute of
Applied Sciences (ACECR), Shahid Beheshti University, Tehran, Iran
Mohaddeseh Khorasanizadeh Department of Chemical Engineering, Sharif
University of Technology, Tehran, Iran
Mohammed Hussein Rafeq Khudhair Laboratory of Agro resources Polymers
and Process engineering (LAPPE), Team of Macromolecular and Organic Chemis-
try, Faculty of sciences, Ibn Tofail University, Kenitra, Morocco
Laboratory of Cement and Quality Control of Amran Cement Plant of Yemen,
Amran, Yemen
Laboratory of Chemistry of Solid State, Faculty of Science, Ibn Tofail University,
Kenitra, Morocco
A. K. Khurana Central Council for Research in Homeopathy, New Delhi, India
Daniel Kibami Department of Chemistry, Kohima Science College (Autonomous)
Jotsoma, Kohima, Nagaland, India
Stamatia Kontogianni Laboratory of Heat Transfer and Environmental Engineer-
ing, Department of Mechanical Engineering, Aristotle University of Thessaloniki,
Thessaloniki, Greece
Raj Kumar Vallabhbhai Patel Chest Institute, University of Delhi, New Delhi,
India
xxxiv Contributors
S. Lakshmana Prabu Department of Pharmaceutical Technology, Bharathidasan

Institute of Technology, Anna University, Tiruchirappalli, Tamil Nadu, India
Sze-Mun Lam Department of Environmental Engineering, Faculty of Engineering
and Green Technology, Universiti Tunku Abdul Rahman, Kampar, Perak, Malaysia
Christof Lanzerstorfer University of Applied Sciences Upper Austria, Wels,
Austria
Ronald Kondo Lembang Faculty of Natural Science and Engineering Technology,
University of Halmahera, Tobelo, North Mollucas, Indonesia
Hayat Lionboui Department of Economics and Rural Sociology, National Institute
of Agricultural Research, Research Center of Tadla, Beni Mellal, Morocco
Laboratory of Environment and Valorization of Agro-Resources, Sultan Moulay
Slimane University, Beni Mellal, Morocco
Esther Lizasoain-Arteaga GITECO Research Group, Universidad de Cantabria,
Santander, Spain
Israel López Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias
Químicas, Laboratorio de Materiales I, San Nicolás de los Garza, Nuevo León,
Mexico
Sandra Manoela Dias Macedo Departamento de Farmacociências, UFCSPA,
Porto Alegre, Brazil
Hisham A. Maddah Department of Chemical Engineering, King Abdulaziz
University, Rabigh, Saudi Arabia
Morteza Mahmoudi Energy Research Institute, Sharif University of Technology,
Tehran, Iran
Arunabha Majumder School of Water Resources Engineering, Jadavpur Univer-
sity, Kolkata, West Bengal, India
All India Institute of Hygiene and Public Health, Govt. of India, Kolkata, India
R. K. Manchanda Central Council for Research in Homeopathy, New Delhi, India
Jubhar C. Mangimbulude Faculty of Natural Science and Engineering Technol-
ogy, University of Halmahera, Tobelo, North Mollucas, Indonesia
Meghna Manjunath R & D Centre, Department of Biotechnology Engineering,
S. Manna Centre for Interdisciplinary Research and Education, Kolkata, India
Asis Mazumdar School of Water Resources Engineering, Jadavpur University,
Contributors xxxv
Gordon McKay Division of Sustainable Development, College of Science and

Engineering, Hamad Bin Khalifa University, Qatar Foundation, Doha, Qatar
Subhash Medhi Department of Bioengineering and Technology (GUIST), Gauhati
University, Guwahati, India
Souad Mehalaine Department of Natural and Life Sciences, Faculty of Exact
Sciences and Natural and Life Sciences, Larbi Tebessi University, Tebessa, Algeria
Larissa Meincke Universidade Feevale, Novo Hamburgo, Brazil
Mustapha Melhaoui Faculty of Science, Department of Physics, Team: Materials,
Morocco
Bahia Meroufel Faculty of Technology, University Abou Bekr Belkaïd of
Tlemcen, Tlemcen, Algeria
Radin Mohamed Micro-Pollutant Research Centre (MPRC), Department of Water
and Environment Engineering, Faculty of Civil and Environmental Engineering,
University Tun Hussein Onn Malaysia (UTHM), Parit Raja, Johor, Malaysia
Abdul Rahman Mohamed School of Chemical Engineering, Universiti Sains
Malayisia, Engineering Campus, Nibong Tebal, Pulau Pinang, Malaysia
Noor Mohammad Department of Law, Green University of Bangladesh, Dhaka,
Bangladesh
Alsharifa Hind Mohammad Water, Energy and Environment Center, The Univer-
sity of Jordan, Amman, Jordan
Sathaporn Monprapussorn Department of Geography, Faculty of Social
Sciences, Srinakharinwirot University, Bangkok, Thailand
Jean-Hude E. Moudingo FAO Cameroon Representation Mangrove Project and
Cameroon Wildlife Conservation Society (CWCS), CWCS Coastal, Forests and
Mangrove Programme, Mouanko, Littoral Region, Cameroon
Nicolas Moussiopoulos Laboratory of Heat Transfer and Environmental Engineer-
ing, Department of Mechanical Engineering, Aristotle University of Thessaloniki,
Thessaloniki, Greece
Jitendra Kumar Nagar Vallabhbhai Patel Chest Institute, University of Delhi,
New Delhi, India
Richa Dave Nagar Amity Institute of Environmental Sciences, Amity University,
Noida, Uttar Pradesh, India
Soumya Nair Microbial Biotechnology Laboratory, School of Biosciences and
Technology, VIT University, Vellore, Tamil Nadu, India
P. Nandy Centre for Interdisciplinary Research and Education, Kolkata, India
xxxvi Contributors
D. Nayak Central Council for Research in Homeopathy, New Delhi, India

Modou Njei WABSA West Africa Study Birds Association, Banjul, Gambia
Saeed Nojavan Department of Analytical Chemistry and Pollutants, Shahid
Beheshti University, G. C., Evin, Tehran, Iran
Efaq Ali Noman Faculty of Applied Sciences and Technology (FAST), Universiti
Tun Hussein Onn Malaysia, Pagoh, Johor, Malaysia
O. M. Olofinnade Covenant University, Ota, Ogun State, Nigeria
Daniela Montanari Migliavacca Osório Programa de Pós-graduação em
Qualidade Ambiental, Universidade Feevale, Novo Hamburgo, RS, Brazil
A. Ouigmane Laboratory of Spectro-Chemistry Applied and Environment,
University Sultan MoulaySlimane, BeniMellal, Morocco
Laboratory of Environment and Valorization d of Agro-Resources, University Sultan
MoulaySlimane, BeniMellal, Morocco
Transdisciplinary Team of Analytical Sciences for Sustainable Development,
University Sultan MoulaySlimane, BeniMellal, Morocco
K. Ouzaouit REMINEX research center, Groupe Managem, Marrakech/Medina,
Morocco
Somnath Pal School of Water Resources Engineering, Jadavpur University,
Sudipta Pal Nutritional Biochemistry and Toxicology Laboratory, Department of
Human Physiology, Tripura University (A Central University), Suryamaninagar,
West Tripura, India
Sukanchan Palit Department of Chemical Engineering, University of Petroleum
and Energy Studies, Energy Acres, Dehradun, Uttarakhand, India
Rashmi Paliwal Institute of Environmental Studies, Kurukshetra University,
Kurukshetra, India
Niraj Singh Parihar Department of Civil Engineering, Jaypee University of
Information Technology, Waknaghat, Himachal Pradesh, India
Musarrat Parween Water Programme, National Institute of Advanced Studies,
Bengaluru, Karnataka, India
Anju Patel Faculty of Civil Engineering, Shri Ramswaroop Memorial University,
Barabanki, India
Amulya A. Patil R & D Centre, Department of Biotechnology Engineering,
Contributors xxxvii
Satish Patil Department of Environmental Sciences, Dr. Babasaheb Ambedkar

B. K. Paul Centre for Interdisciplinary Research and Education, Kolkata, India
Hamid M. Pouran Faculty of Science and Engineering, University of Wolver-
hampton, Wolverhampton, UK
N. Priyadarshini Department of Chemistry, SSN College of Engineering,
Kalavakkam, Tamil Nadu, India
Dunja Prokić Faculty of Environmental Protection, University Educons, Sremska
Kamenica, Serbia
R. C. Pullar Department of Materials and Ceramic Engineering, Department of
Physics, CICECO – Aveiro Institute of Materials, University of Aveiro, Aveiro,
Portugal
P. N. Puniya Department of Environmental Sciences, Dr. Babasaheb Ambedkar
Abdul Qadir College of Earth and Environmental Science (CEES), Faculty of
Science, University of the Punjab, Lahore, Pakistan
R. M. S. Radin Mohamed Micro-Pollution Research Centre (MPRC), Department
of Water and Environmental Engineering, Faculty of Civil and Environmental
Engineering, Universiti Tun Hussein Onn Malaysia, Parit Raja, Johor, Malaysia
Mirzanur Rahman Department of Information Technology (GUIST), Gauhati
University, Guwahati, India
A. Raj Department of Forestry, College of Agriculture, I.G.K.V, Raipur, CG, India
A. L. Ramanathan School of Environmental Sciences, Jawaharlal Nehru Univer-
sity, New Delhi, India
Manviri Rani Department of Chemistry, Dr B R Ambedkar National Institute of
Technology, Jalandhar, Punjab, India
Nisha Rani Department of BioSciences, Himachal Pradesh University, Shimla,
India
T. E. Rasimphi Department of Ecology and Resource Management, University of
Venda, Thohoyandou, South Africa
Mohd Adib Mohammad Razi Micro-Pollutant Research Centre (MPRC), Depart-
ment of Water and Environment Engineering, Faculty of Civil and Environmental
Engineering, University Tun Hussein Onn Malaysia (UTHM), Parit Raja, Johor,
Malaysia
M. Rengasamy Department of Petrochemical Technology, Bharathidasan Institute
of Technology, Anna University, Tiruchirappalli, Tamil Nadu, India
xxxviii Contributors
Yahia Rharrabti Polydisciplinary Faculty of Taza, Taza, Morocco

Jan W. Rijstenbil AE3 Consultancy, Yerseke, The Netherlands
Maria Romero-Gonzalez Department of Geography, University of Sheffield,
Sheffield, UK
Michele S. G. Rosa Pontifícia Universidade Católica do Rio Grande do Sul –
PUCRS, Porto Alegre, Brazil
C. Rosin Agence nationale de sécurité sanitaire de l’alimentation, de
l’environnement et du travail (Anses) Direction de l’Evaluation des Risques, Unité
évaluation des risques liés à l’eau, Maisons-Alfort Cedex, France
Pankaj Kumar Roy School of Water Resources Engineering, Jadavpur University,
Malabika Biswas Roy Women’s College, Calcutta, Kolkata, India
Anand Sagar Department of BioSciences, Himachal Pradesh University, Shimla,
India
Vipin K. Saini School of Environment and Natural Resources, Doon University,
Dehradun, Uttrakhand, India
Muhammad Shabery Sainudin Micro-Pollution Research Centre (MPRC),
Department of Water and Environmental Engineering, Faculty of Civil and Envi-
ronmental Engineering, Universiti Tun Hussein Onn Malaysia, Parit Raja, Johor,
Malaysia
Junaid Saleem Division of Sustainable Development, College of Science and
Niloufar Salehi Energy Research Institute, Sharif University of Technology,
Tehran, Iran
P. Sankar Ganesh Department of Biological Sciences, BITS Pilani, Hyderabad
Campus, Hyderabad, Telangana, India
Debanjan Sannigrahi Advanced Management Institute for Training and Achieve-
ment (AMITA), Mumbai, Maharashtra, India
A. K. Sannigrahi Proof & Experimental Establishment (PXE), Defence Research
and Development Organization, Balasore, India
Luis A. Sañudo-Fontaneda GICONSIME Research Group, University of Oviedo,
Mieres, Asturias, Spain
Abhishek Saxena Faculty of Civil Engineering, Sri Ramswaroop Memorial
University, Barabanki, Uttar Pradesh, India
S. Sendilvelan Department of Mechanical Engineering, Dr. M.G.R Educational
and Research Institute, University, Chennai, India
Contributors xxxix
Philippe Serp Laboratoire de Chimie de Coordination UPR CNRS 8241,

composante ENSIACET, Université de Toulouse, UPS-INP-LCC, Toulouse Cedex
4, France
Muafia Shafiq College of Earth and Environmental Science (CEES), Faculty of
Science, University of the Punjab, Lahore, Pakistan
Biotechnology and Food Research Centre, PCSIR Laboratories Complex, Lahore,
Pakistan
Usman Bin Shahid Division of Sustainable Development, College of Science and
Apoorva Shankar R & D Centre, Department of Biotechnology Engineering,
Aparajita Shankar School of Environment and Natural Resources, Doon Univer-
sity, Dehradun, Uttrakhand, India
Uma Shanker Department of Chemistry, Dr B R Ambedkar National Institute of
Technology, Jalandhar, Punjab, India
Hardeep Rai Sharma Institute of Environmental Studies, Kurukshetra University,
Kurukshetra, Haryana, India
Kanu Shil Department of Human Physiology, Tripura University, Agartala,
Tripura, India
J. P. Shrivastava Centre of Advanced Studies and Department of Geology,
University of Delhi, New Delhi, India
Saurabh Shukla Faculty of Civil Engineering, Shri Ramswaroop Memorial
University, Lucknow, India
Zia Mahmood Siddiqi Jubail University College, Jubail Industrial City, Saudi
Arabia
Jin-Chung Sin Department of Petrochemical Engineering, Faculty of Engineering
and Green Technology, Universiti Tunku Abdul Rahman, Kampar, Perak, Malaysia
Poonam Singhal Centre for Rural Development and Technology, Indian Institute
of Technology Delhi, New Delhi, India
Indian Institute of Management, Calcutta, India
Sinosh Skariyachan R & D Centre, Department of Biotechnology Engineering,
Salah Souabi Laboratory of Process Engineering and Environment, Faculty of
Sciences and Techniques, Mohammedia, University – Hassan II, Mohammedia,
Morocco
xl Contributors
Lekha Sridhar Consultant - United Nations Environment Programme (UNEP),

New Delhi, India
Nataša Stojić Faculty of Environmental Protection, University Educons, Sremska
Kamenica, Serbia
Snežana Štrbac Faculty of Environmental Protection, University Educons,
Sremska Kamenica, Serbia
Sumathi Suresh Centre for Environmental Science and Engineering, Indian
Institute of Technology Bombay, Mumbai, Maharashtra, India
Anushree Suresh Microbial Biotechnology Laboratory, School of Biosciences and
Technology, VIT University, Vellore, Tamil Nadu, India
Swati School of Environmental Sciences, Jawaharlal Nehru University, New Delhi,
India
Saul Taal Ministry of Agriculture/Research Institute, Banjul, Gambia
Hadi Tabani Department of Environmental Geology, Research Institute of Applied
Sciences (ACECR), Shahid Beheshti University, Tehran, Iran
Vinod Tare Department of Civil Engineering, IIT Kanpur, Kanpur, India
Indu Shekhar Thakur School of Environmental Sciences, Jawaharlal Nehru
University, New Delhi, India
D. Tinarwo Department of Physics, University of Venda, Thohoyandou, South
Africa
Lamin Mai Touray Department of Water Resources, Banjul, Gambia
A. Umamaheswari Department of Pharmaceutical Technology, Bharathidasan
Institute of Technology, Anna University, Tiruchirappalli, Tamil Nadu, India
C. Veluchamy Department of Civil Engineering, Indian Institute of Technology
Guwahati, Guwahati, India
School of Environmental Science, University of Guelph Ridgetown Campus,
Ridgetown, ON, Canada
G. Venkatesan Department of Civil Engineering, Bharathidasan Institute of
Technology, Anna University, Tiruchirappalli, Tamil Nadu, India
Virendra Kumar Vijay Centre for Rural Development and Technology, Indian
Institute of Technology, New Delhi, India
Ali Vosoogh Department of Civil Engineering, Iran University of Science and
Technology, Tehran, Iran
Wenqin Wang School of Agriculture and Biology, Shanghai Jiao Tong University,
Shanghai, China
Contributors xli
A. N. Welfrad Micro-pollution Research Centre (MPRC), Department of Water

and Environmental Engineering, Faculty of Civil and Environmental Engineering,
Universiti Tun Hussein Onn Malaysia, Parit Raja, Johor, Malaysia
D. K. Yadav Department of Farm Forestry, Sarguja University, Ambikapur,
Chhattisgarh, India
Kaan Yetilmezsoy Department of Environmental Engineering, Faculty of Civil
Engineering, Yildiz Technical University, Istanbul, Esenler, Turkey
Sherif A. Younis Analysis and Evaluation Department, Egyptian Petroleum
Research Institute, Nasr City, Cairo, Egypt
Laboratoire de Chimie de Coordination UPR CNRS 8241, composante ENSIACET,
Université de Toulouse, UPS-INP-LCC, Toulouse Cedex 4, France
A. Zeghnoun Agence nationale de santé publique 12 rue du Val d’Osne 94415,
Saint Maurice Cedex, France
Mohamed Amine Zenasni Faculty of Technology, University Abou Bekr Belkaïd
of Tlemcen, Tlemcen, Algeria
Part I
Major Environmental Issues and Problems
Assessment of Some Aspects of
Provisioning Sewerage Systems: A Case 1
Study of Urban Agglomerations in Ganga
River Basin
Saurabh Shukla and Vinod Tare
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Cost Estimates of Sewerage Systems: Conventional Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Collection of Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Final Cost Estimation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Cost Estimates of Sewerage Systems: Other Approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Sewerage Network . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Sewage Pumping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Sewage Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Estimation of Capex and Opex of Sewerage Network . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Estimation of Capex and Opex for Sewage Pumping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Estimation of Capex and Opex of Sewage Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Findings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Sewerage Network . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Cost of Sewage Pumping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Cost of Sewage Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Cost Estimation of Complete Sewerage System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Estimated Costs of Provisioning Sewerage Systems in Major Urban Agglomerations in
Ganga River Basin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Benefits of Provisioning Sewerage Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
S. Shukla (*)
Faculty of Civil Engineering, Shri Ramswaroop Memorial University, Lucknow, India
e-mail: saurabh.shukla2020@gmail.com
V. Tare
Department of Civil Engineering, IIT Kanpur, Kanpur, India
e-mail: vinod@iitk.ac.in
© Springer Nature Switzerland AG 2019 3

C. M. Hussain (ed.), Handbook of Environmental Materials Management,
https://doi.org/10.1007/978-3-319-73645-7_3
4 S. Shukla and V. Tare
Abstract
An appropriate techno-commercial framework is a prerequisite for sustainable
sanitation solutions in urban centers. The first step toward developing such a
framework is to have an assessment of provisioning sanitation systems in eco-
nomic sense. The present study aims at estimating the per capita expenditure on
sewerage system. The energy consumption and footprint are also important along
with expenditure incurred and hence are also estimated separately. Results indi-
cate that footprint for sewage treatment is approximately 0.1 m2 per person which
is one tenth of the size of the toilet. The energy consumption in sewage pumping
and treatment ranges from 0.03 to 0.1 KW-h (kilowatt-hour) which is equivalent
to lighting 30 to 100 watt bulb for 1 h. The total per capita expenditure in availing
sewerage infrastructure is estimated to be in the range INR (Indian Rupee Rates)
1.8–10.8 with an average of INR 3.93 and standard deviation 1.4. The higher
values correspond to towns with very low population density, and the lower
values correspond to very high population densities.
Keywords
Sewerage systems · Sewerage network · Sewage pumping · Sewage treatment ·
Cost estimates · Capex · Opex · Ganga River Basin · Ganga River Basin
Management Plan
Introduction
Consortium of seven IITs (Indian Institute of Technology) has been engaged by the
Government of India to prepare Ganga River Basin Management Plan (GRBMP).
One of the most important challenges of the Consortium is to prepare an action plan
for “unpolluted flow” or “Nirmal Dhara” in all rivers of the Ganga Basin. The main
approach to achieve the ultimate objective of “Nirmal Dhara” has been to identify
the type of polluting wastes, their sources of generation (point and nonpoint
sources), and the techno-economic feasibility of collecting and treating them for
their safe environmental discharge and/or possible recycle or reuse. Figure 1 illus-
trates the main identification results and the tasks.
Among the point sources, urban and industrial wastewaters are the major sources
of pollution (Luzio et al. 2003), needing immediate remediation. In consideration of
the magnitude of domestic wastewater generation from different urban locales, urban
settlements are divided into Class I towns (having a population over 100,000) and
Class II towns (having a population between 50,000 and 100,000) (RBI 2003). The
following main steps concerning sewerage infrastructure for medium to long term
(over the next 25 years) are considered essential.
1. Complete stoppage of the discharge of sewage, either treated or untreated, from

Class I and Class II towns to any river.
2. All sewage generated in Class I and Class II towns of GRB needs to be collected
and treated up to the tertiary level with treated effluent standards of Biochemical
1 Assessment of Some Aspects of Provisioning Sewerage Systems: A Case. . . 5
Fig. 1 Types and sources of wastes and main identification tasks (IIT GRB 2013)
Oxygen Demand (BOD) <10 mg/L, suspended solids (SS) <5 mg/L, fully
nitrified effluent, phosphorous <0.5 mg/L, and fecal coliform (FC) <230/100 mL.
3. The tertiary-treated water should be reused for various non-potable purposes,
such as industrial, irrigation, horticultural, and noncontact/non-potable domestic
use. Unused treated water may be utilized for groundwater recharge but only via
surface storages and subsequent infiltration and percolation through soil.
These measures are essential to overcome the declining state of urban wastewater
management in GRB. Although ample amount of money and efforts have been spent
in Ganga Action Plan over the past few decades, the overall achievement has been
limited. And, yet, the same approach has persisted over the years, leading to a
general disillusionment and cynicism. This attitudinal blockade is illustrated in
Fig. 2.
But such despondency and cynicism can be easily overcome if wastewater is
considered as a “resource” rather than as “dirt.” By adequately treating wastewater
and reusing it instead of dumping the untreated or partially treated wastewater to
sully the environment, urban wastewater treatment can achieve “zero liquid dis-
charge” (ZLD) and recover the value of water as a “resource” (Heijman et al. 2009;
Oren et al. 2010). However, costs and benefits of such strategies need to be
delineated in quantitative terms to convince the policy makers (Dodane et al.
2012). It is to satisfy this end that the present study was conducted.
The genesis of this study has been the recommendations of the Environmental
Quality and Pollution (EQP) Group of the Consortium of seven IITs preparing the
Urban Local
Bodies
Unpolluted Expensive/ cannot afford
Flow Unaffordable/Energy
Extensive 1 Paisa per Liter for
Warrants Zero ZLD Vs
Discharge Cynical
Attitude Expensive
Arguments are Household
STPs water treatment
Unsatisfactory
Fig. 2 Schematic representation of attitudinal blockade in managing urban sewerage infrastructure
Ganga River Basin Management Plan to have full coverage of sewerage systems in
all urban agglomerations in the basin. It is important to have appropriate ballpark
estimates of expenditure on provisioning sewerage systems and the tangible and
intangible benefits that would accrue. A complete sewerage system includes sewer-
age network, sewage pumping/lifting, and sewage treatment. A study about the
urban centers in India based on population estimates of 2008 from 2001 census by
the Central Pollution Control Board (CPCB), New Delhi reports that capacity to
partially treat only 11,787 MLD (million liters per day) sewage (out of 38,524 MLD
generated) exists in the country (CPCB 2009). Most of these sewage treatment plants
(STPs) do not perform satisfactorily for various reasons including grossly inadequate
sewerage network and sewage pumping, and a very small fraction of sewage gets
treated to the regulatory standards, while most of the sewage finds its way directly or
indirectly into the water bodies. Thus, it would not be an exaggerated statement to
say that most water supplies in the country are through highly polluted water bodies
including rivers. As such it is necessary to have an estimate of expenditure on
sewerage infrastructure for full coverage of urban agglomerations in the country,
in general, and Ganga River Basin (GRB) in particular.
Cost Estimates of Sewerage Systems: Conventional Approach
The Central Public Health and Environmental Engineering Organisation

(CPHEEO), Ministry of Urban Development (CPHEEO 2013), provides the follow-
ing for cost estimates of sewerage systems.
(a) Capital costs shall include all the cost such as civil construction, equipment
supply and erection costs, land purchase costs, engineering design and supervi-
sion charges, and interest charge on loan.
(b) Operation and maintenance cost after the project is started shall consider amor-
tization and interest charges on capital borrowing, expenditure made on staff,
chemicals, energy, transport, repair work, all the equipment/tools, insurance, and
overheads.
According to the manual, the planning should start with the preparation of City
Master Plan (CMP) and City Sanitation Plan (CSP) which should form the base of
the sewerage system project. Presently very few towns have prepared CMPs and
CSPs. And most CSPs are based on inadequate data and information. Use of
GIS-based information systems is rare.
Collection of Information
To calculate the cost of the sewerage systems, all the basic information is required to
be collected. Some of the essential information/data includes:
(a) Topography of the area to be covered for the design of sewers and location of
sewage treatment works, outfall, and disposal works
(b) Subsoil conditions, such as the strata likely to be found and groundwater table
level
(c) Structures like storm drain and appurtenances, house connections for water supply
and sewerage, electricity supply lines and telephone cables, gas pipelines, etc.
(d) Sewerage master plan, long-term comprehensive development plans for cities
and towns, urban planning, city planning area, urbanization zone, urbanization
control area, land use plan, road plan, urban development as rezoning, residential
estates, industrial complexes, etc.
(e) Population data and quantification of sewer generation, water supply data, etc.
After the collection of the aforementioned information, several reports like

feasibility reports, pre-feasibility reports, and identification reports are to be made.
This kind of work generally ends with the executive summary report which covers
the project’s essential features, basic strategy, approach adopted in developing the
project, and the salient features of financial and administrative aspects.
Final Cost Estimation
CPHEEO (2013) recommends that cost estimation of each component of the project
is prepared and annual requirement of funds for each year is worked out; due
allowance should be made for physical contingencies and annual inflation. This
exercise results in arriving at total funds required annually for the execution of the
project. Further it is required to prepare recurring annual costs of the project for
the next few years (say 10 years) covering operation and maintenance expenditure
for the entire system (staff, chemicals, energy, spare parts and other materials for
system operation, transportation, etc.). The cost estimates are prepared considering
the following points.
(a) Outlining the basic assumptions made for unit prices, physical contingencies,
price contingencies, and escalation
(b) Summarizing the estimated cost of each component for each year till its
completion and working out total annual costs to know annual cash flow
requirements
(c) Estimating foreign exchange cost if required to be incurred
(d) Working out the per capita cost of the project on the basis of design population
and cost per unit of sewage treated and disposed and comparing these with the
government norms, if any
Once the estimation of cost of sewerage systems is completed, the need for an
institutional and financial plan rises which needs the identification of responsible and
capable organization which can be trusted for the completion of the project and also
the identification of all sources of funds for implementation of the project, indicating
year-by-year requirements from these sources, to meet expenditure as planned for
completing the project as per schedule, stating how the interest during construction
period will be paid, or whether it will be capitalized and will be paid in loan,
explaining the procedures involved in obtaining funds from the various sources.
Cost Estimates of Sewerage Systems: Other Approaches
The conventional approach followed is to prepare bill of quantities (BOQ) for various
items and use unit costs to get the total expenditure. However, this approach requires
availability of detailed design and specifications. In most cases at the planning stage, it
is not possible to prepare BOQs. Mostly thumb rules and past experiences are used.
Most of these thumb rules are not available in any published literature but are
available in organizations involved in planning and execution of sewerage systems.
Sewerage Network
Sewerage network includes sewers, manholes, and other appurtenances (Bennis

et al. 2003; Semadeni-Davies et al. 2008). In order to have a cost estimate, the first
step is to compile information on lengths of various sizes of sewers, number and
sizes of manholes, and unit costs. Generally, the unit costs can be easily worked out
for different settings. However, the other information is generally not available,
presenting the need for other approaches. For example, in the estimation of sewerage
network costs, it is assumed that cost of pipes is about 15% of the total network cost.
But the use of this approach requires that total length of various diameter pipes be
known. Again, as a thumb rule, it is assumed that 70–80% of total sewer length is of
150 and 200 mm diameter sewers. It is not possible to estimate the total length unless
the detailed plan of the town is available. Essentially no published information could
be found on this. Thus, it is necessary to develop methods for estimating lengths of
various sizes of sewers contributing to sewerage network and operation and main-
tenance costs.
Sewage Pumping
The major components of sewage pumping stations include pumps, civil works and
miscellaneous material supplies such as inlet and outlet pipes, fittings such as valves,
connectors, pipes, etc. (Bertrand-Krajewski et al. 1995; Dodane et al. 2012). In order
to estimate the pump sizes, it is necessary to get the information on the quantity of
sewage to be pumped and the pumping head. No published literature could be found
to arrive at the pump sizes without a detailed design of sewer networks. For other
items, thumb rules are used by the practicing engineers and professionals. For
example, it is assumed (based on market survey) that civil construction cost of
pumping stations is about 10% of the cost of the pumps. Similarly, the cost of
miscellaneous material supplies is assumed as 1–2% of the cost of pumps. These
estimations are based on BOQs obtained through various agencies. The operation
and maintenance costs of pumping stations are essentially those of energy consump-
tions. Other costs are minor costs and are assumed to be 1% of the energy bill.
Sewage Treatment
Estimation of sewage treatment costs requires information on treatment technology,

unit costs, and quantity of sewage to be treated. This can generally be done without a
detailed design as unit costs of various treatment technologies with their perfor-
mance are available (Tare and Bose 2009; IIT_GRB 2010). Also estimation of
quantity of sewage can be done based on population and water supply rates
(CPHEEO Manual 2013). Similarly, operation and maintenance costs for various
types of treatment technologies are also available (IIT_GRB 2010).
The conventional approach for estimation of expenditure on provisioning sewer-
age systems requires detailed specifications of sewerage network and sewage
pumping stations. Requisite information to arrive at such information is often not
available at the planning stage. This warrants exploring other approaches for ball-
park estimates of sewerage systems at the planning stage which do not depend on
detailed specifications. Practicing engineers, professionals, and consulting organi-
zations engaged in planning and developing proposals adopt thumb rules based on
past experiences and the data available from various detailed project reports. Such
data are generally not accessible to all. It is plausible to develop approaches based on
a huge amount of information available on sewerage systems in India with urban
local bodies, consulting firms, and practicing engineers and professionals for ball-
park estimates of sewerage systems with some reasonable assumptions.
The state of sewerage infrastructure in India, in general, and in Ganga River Basin in
particular is very poor. This is believed to be due to the lack of adequate resources
required to develop such infrastructure. In the past few decades, the Government of
India launched several large programs such as Ganga Action Plan (GAP), Yamuna
Action Plan (YAP), Jawaharlal Nehru National Urban Renewal Mission (JNNURM),
etc. to pump in huge funds. However, this has been done without systemic assessment of
the actual resources required and to a large extent on an ad hoc planning. Also, very little
planning has been done to fill the huge gap and for operation and maintenance of the
assets created. As a result, not much benefit has been seen on ground, and no sustainable
model is in the sight. It is very important that an appropriate techno-commercial
framework is developed for sustainable sewerage system for the urban centers.
The present study is a part of this larger framework and aims at estimating the
financial layout for provisioning sewerage infrastructure in all Class I and Class II
towns of the Ganga River Basin (GRB) with the objective of recycling and reusing
sewage along with assessment of freshwater savings that could facilitate in the
management of environmental flows (e-flows) in the rivers. The following specific
objectives are set for this study to achieve this goal.
1. Develop suitable methodology for obtaining ballpark estimates for full coverage
of sewerage network in Class I and Class II towns of GRB.
2. Develop suitable framework for obtaining ballpark estimates for sewage pumping.
3. Obtain ballpark estimates of capital investments for provisioning sewerage infrastruc-
ture and annualized expenditure toward capital (Capex) and sustainable operation and
maintenance (Opex) of such infrastructure in all Class I and Class II towns of GRB.
4. Assess financial implications of provisioning sustainable sewerage infrastructure
on individuals residing in the urban agglomerations of GRB.
5. Assess freshwater savings that can assist in managing environmental flows
(e-flows) in the rivers.
Methodology
Sewerage infrastructure includes (i) sewer network, (ii) sewage pumping, and (iii)
sewage treatment plants. Estimation of capital and operation and maintenance costs
for these three components has been worked out separately for all Class I and Class II
towns in Ganga River Basin (GRB). The following sections briefly describe the
methodology adopted.
Estimation of Capex and Opex of Sewerage Network
This involves estimation of the length of sewer pipes of different diameters and cost
of laying unit length including the supply of materials, barricading the area, timber-
ing in trenches, excavation of earth, laying, jointing of sewer lines, surface relaying,
costs of manholes, labors, dewatering, etc.
An empirical approach is followed to arrive at these costs. Data from approxi-
mately 45 different urban locations where sewer networks have been laid or
designed is gathered from various local bodies and consulting firms. This data
included population, area covered, lengths of various diameter pipes, bill of quan-
tities (BOQs), cost estimates, and total cost of the project. The BOQs and cost
estimates had all the details which are required for the estimation of sewerage
network costs.
Several approaches, outlined as follows by which unit costs could be worked out,
were attempted.
Approach I. The unit cost (average per meter length of sewer laid including all
items in BOQs) is taken as the total cost of the sewerage network project divided by
the total sewer length (all diameter sewers). This cost comes around INR 4000–5500
per meter of the sewer length. This is the cost of laying the fresh sewer lines with
minimal hindrances as it includes only the supply of materials, barricading the area,
timbering in trenches, excavation of earth, laying, jointing of sewer lines, surface
relaying, costs of manholes, labors, dewatering, etc. In general, this unit cost could
be considered for greenfield projects, i.e., for newly developed areas or colonies
where there are no obstructions (rail lines; roads; buildings; other infrastructure
networks such as water supply lines, cable networks, etc.; encroachments and/or
monuments of historical or religious importance; etc.). This unit cost increases to
INR 6500–10,000 when some miscellaneous items like crossing of railway lines,
crossing through drains, some extra sewer lines due to uncertainties in estimation of
total sewer lengths, adoption of trenchless technology for some area, dismantling of
roads, relaying of roads, etc. are considered. The unit costs considered in this study
are as follows.
• INR 5000 for greenfield sites

• INR 8000 for sites involving few hindrances and moderate degree of congestion
• INR 10,000 for sites involving many hindrances and high degree of congestion
Approach II. Unit cost of the sewer pipes can be estimated with a high degree of
confidence and does not vary much from one site to another. Thus, for various
projects, cost estimates were made based on BOQs of various items, and percentage
of the cost incurred in supply of sewer pipes was computed. The cost of supply of
sewer pipes ranged between 12% and 15% of the total amount of the sewer line
laying, jointing, labors, excavation of soil and manholes, etc. Based on this, the total
cost of sewerage network can be taken as “x/0.15,” where x is the cost of supply of
sewer pipes. In this study, this is only used for cross validation of the costs estimated
using “Approach I” described earlier.
Approach III. In this approach, unit cost of various sizes of pipes is calculated
based on BOQs and keeping provision for some exigencies based on tips received
from practicing engineers. The average unit cost is worked out through weighted
average based on percentage lengths of various-sized pipes in the total sewer
network length. This approach is also used for cross validation of the costs estimated
using “Approach I” described earlier.
Operation and maintenance (Opex) costs are estimated based on thumb rules and
taken as 1.5% of Capex as per the survey conducted by the Water and Sanitation
Program (DeFrancis 2011).
Estimation of Capex and Opex for Sewage Pumping
Sewage pumping involves pumps, pumping stations, and some miscellaneous material
supplies such as valves, inlet and outlet pipes, pipe fittings, etc. Pump capacity is
estimated based on (i) total daily sewage flow, (ii) average 12 h pumping in a day,
(iii) pumping head assuming 1 in 80 slope of the trunk sewer, and length of the trunk
sewer as the diagonal dimension of the area served by sewerage network assuming the
shape of town to be a square. Cost of the pumps is estimated based on market survey and
information provided by practicing engineers as INR 25,000/KW. Cost of miscellaneous
material supplies such as valves, inlet and outlet pipes, pipe fittings, etc. generally varies
in the range of 1–2% of the pump cost. To have conservative estimates, a value of 2% is
assumed in this study. The estimated cost of pumping stations is 10% of the cost of
pumps based on thumb rule generally used by practicing engineers and consulting firms.
Opex cost of sewage pumping is computed based on energy consumption for
running the pumps considering prevailing average electricity tariff (INR 6 per KW-h
or a unit of electricity consumed). In addition, 1% of energy bill for running the
pumps is considered as other miscellaneous Opex for sewage pumping based on
thumb rule generally used by practicing engineers and consulting firms.
Estimation of Capex and Opex of Sewage Treatment
Estimation of cost of sewage treatment has been done considering that the sewage
treatment plants will use sewage as source of water and produce water that would be
suitable for reuse for many purposes including that for nonhuman contact domestic
activities such as toilet flushing, car/floor washing, air conditioning, other bulk
commercial uses, horticulture and gardening, and maintaining surface water bodies
for recreation and groundwater recharging. Typically, the treatment would be done in
three stages, namely, primary, secondary, and tertiary. For cost estimations, most
widely used and time-tested conventional activated sludge process (ASP) is consid-
ered at the secondary level with sludge dewatering adopting filter press or centrifuge
instead of sludge drying beds. At the tertiary level, coagulation-flocculation followed
by filtration is considered for cost estimation purposes.
Much of the information used for cost estimation is adopted from the report
prepared by Consortium of seven IITs preparing GRBMP (IIT_GRB Report 2010).
Relevant information is presented in Table 1.
Findings
Sewerage Network
Estimation of costs of sewerage network calls for complete layout including

lengths of sewers of various diameters, number and sizes of manholes, ground
conditions (type of soil/rock, water table, present usage, etc.), depth of sewers, etc.
Table 1 Details of information used in cost estimation of sewage treatment

Item
number Item Value Range
1.0 Capital cost, millions of INR/MLD
1.1 Total capital cost (secondary + tertiary) 11 10–12.5
1.2 Civil works, % of total capital costs 60
1.3 E&M works, % of total capital costs 40
2.0 Land requirement, ha/MLD
2.1 Average area, ha/MLD 0.09
Secondary treatment + secondary sludge handling
2.2 Average area, ha/MLD 0.01
Tertiary treatment + tertiary sludge handling
2.3 Total area, ha/MLD 0.10 0.08–0.1
Secondary + tertiary treatment
3.0 Operation and maintenance cost, millions of INR/MLD/year
3.1 Cost of energy
3.1.1 Avg. technology power requirement, KW-h/d/MLD 200 180–220
Secondary treatment + secondary sludge handling
3.1.2 Avg. technology power requirement, KW-h/d/MLD 1
Tertiary treatment + tertiary sludge handling
3.1.3 Avg. non-technology power req., KW-h/d/MLD 7 5–7.5
Secondary treatment
3.1.4 Avg. non-technology power req., KW-h/d /MLD 0.2
Tertiary treatment
3.1.5 Total daily power requirement (avg.), KW-h/d/MLD 208.2
3.1.6 Daily power cost (at Rs.6.0 per KW-h), INR/MLD/h 52.05
(including standby power cost)
3.1.7 Yearly power cost, millions of INR/MLD/year 4.56
3.2 Cost of repairs
3.2.1 Civil works per annum, as % of civil work cost 3
3.2.2 E&M works, as % of E&M work cost 1
3.2.3 Civil works maintenance, millions of INR/MLD/year 0.2
3.2.4 E&M work maintenance, millions of INR/MLD/year 0.04
3.2.5 Annual repair costs, millions of INR/MLD/year 0.24
3.3 Cost of chemicals
3.3.1 Total chemical cost, millions of INR/MLD/year 0.61
3.4 Manpower cost
3.4.1 Manager, millions of INR per annum (pa) (1 No.) 0.42
3.4.2 Chemist/engineer, millions of INR pa (1 No.) 0.42
3.4.3 Operators, millions of INR pa (6 at INR 15,000 pm) 1.08
3.4.4 Skilled technicians, millions of INR pa (6 at INR 12,000 pm) 0.864
3.4.5 Unskilled personnel, millions of INR pa (6 at INR 10,000 0.72
pm)
3.4.6 Total salary costs, millions of INR/MLD/year 3.5
3.4.7 Benefits (50% of total salary), millions of INR/MLD/year 1.76
(continued)
Table 1 (continued)
Item
number Item Value Range
3.4.8 Salary + benefits, millions of INR/MLD/year 5.26
3.4.9 Total annual O&M costs, millions of INR/MLD/year 1.4
4.0 NPV of capital + O&M cost for 30 years, millions of 22.34
INR/MLD/year
Total treatment cost, INR/KL 7.9
Gathering such type of information is a humungous task and is generally not

available prior to preparation of a detailed project report (DPR). Hence, an empirical
approach is followed to arrive at ballpark estimates.
Estimation of Sewer Length

Data from 45 different Indian urban locations where sewer networks have been laid or
designed is gathered from various local bodies, consulting firms, and practicing
engineers. Based on these data, empirical correlations are examined to first estimate
the lengths of various diameter sewers as a function of area covered and population
served. The outcome of such correlations is presented in Table 2 and Figs. 3, 4, and 5.
It may be observed here that, except for 300 and 1200 mm diameter pipes, the
relationships developed are statistically significant at 95% confidence level
(Table 2). The correlations developed are considered acceptable for arriving at
ballpark estimations of lengths of laterals and branch sewers not more than
750 mm diameter. For main or trunk sewers, the length could be approximately
taken as diagonal of the town assuming the town area to be of square shape. The
trunk sewer is designed for (i) total sewage generated from a town, (ii) maximum
depth of flow as three fourths of the diameter of sewer, (iii) slope of 1 in 1000,
(iv) Manning’s coefficient as 0.01 for HDPE (high-density polyethylene) pipe,
(v) infiltration at 10%, and (vi) peak factor 2.25 as per CPHEEO Manual (CPHEEO
2013). Branch sewers are considered to be of maximum 750 mm diameter or one
available size lower than the size of the trunk sewer, whichever is lower. The
population of Cass I and Class II towns has been taken from Census 2011 data
(Census 2011). Water supply rate is taken as 135 l per capita per day (CPHEEO
2013), and sewage generation is assumed to be 80% of the water supply. Information
on area of towns is obtained from local bodies. With the information given here and
empirical equations reported in Table 2, lengths of various diameter pipes were
calculated for Class I and Class II towns of GRB to arrive at ballpark estimates of
total length of sewerage network.
A comparison of the estimated percentage distribution of lengths of various
diameter sewers for a typical Class I town whose actual data was available is
presented in Fig. 6. Results suggest that the estimated and actual distribution
match reasonably well for the purpose of arriving at ballpark estimates.
The correlations could be substantially improved if actual data on road lengths is
also made available so that lengths of sewers are considered as function of road
Table 2 Outcome of empirical correlations to estimate lengths of various diameters of sewers as a

function of area covered and population served
Value of R for
statistically
Length of sewer in Km as a Coefficient significant
Diameter function of area covered in Number of correlation at
S of sewer km2 and population served of data correlation 95% confidence
No. in mm in thousands points (R) level
01 150 5.045 * (A0.284) * (P0.632) 45 0.828 0.294
02 200 4.420 * (A0.523) * (P0.485) 45 0.916 0.294
03 250 0.116 * (A0.533) * (P0.209) 45 0.743 0.294
04 300 0.182 * (A0.481) * (P0.358) 45 0.807 0.294
05 350 0.817 * (A0.185) * (P0.336) 39 0.260 0.316
06 400 0.167 * (A0.426) * (P0.228) 41 0.554 0.308
07 450 0.480 * (A0.299) * (P0.326) 44 0.571 0.297
08 500 0.005 * (A0.850) * (P0.263) 33 0.755 0.344
09 600 0.041 * (A0.650) * (P0.021) 42 0.628 0.304
10 700 0.007 * (A0.803) * (P0.087) 25 0.742 0.396
11 750 0.407 * (A0.305) * (P0.170) 33 0.600 0.344
12 800 0.190 * (A0.404) * (P0.141) 31 0.438 0.355
13 900 0.012 * (A0.809) * (P0.134) 35 0.666 0.334
14 1000 0.142 * (A0.526) * (P0.530) 29 0.841 0.367
15 1100 1.487 * (A0.319) * (P0.797) 33 0.811 0.355
16 1200 0.636 * (A0.201) * (P0.552) 11 0.394 0.602
17 1400 0.456 * (A0.386) * (P0.309) 11 0.721 0.602
18 1600 0.611 * (A0.414) * (P0.416) 12 0.726 0.576
length and population density. It is to be noted that this approach is not to be used for
obtaining actual lengths of sewers in a town.
Estimation of Costs
Cost for sewerage network has been estimated by multiplying the weighted average
(based on percentage distribution of various diameter sewers shown in Fig. 6) unit
cost per meter length of sewer laid (including all items in BOQs) with the total length
of sewer network estimated as given in the previous section. The details of typical
estimated unit costs for various diameter sewers as per BOQ are presented in Table 3
and Fig. 7.
The estimated weighted average unit cost varies from INR 4000 to 5000 per meter
of the sewer length for various towns. This is the cost of laying the fresh sewer lines
with minimal hindrances as it includes only the supply of materials, barricading the
area, timbering in trenches, excavation of earth, laying, jointing of sewer lines,
surface relaying, costs of manholes, labors, dewatering etc. Typical breakup of
average unit costs as per BOQ among major components is presented in Fig. 8.
However, considering low to moderate levels of hindrances in Class I and Class II
towns, average unit costs are considered to be INR 7000 and INR 6000 per m length
a 50 b 250
40 200
Estimated, km
Estimated, km
30 150
20 100
10 50
0 0
0 10 20 30 0 50 100 150
Calculated, km Calculated, km
c 16 d 12
10
12
Estimated, km
Estimated, km
8
8 6
4
4
2
0 0
0 4 8 12 0 2 4 6 8
e 6 f 10
5 8
Estimated, km
Estimated, km
4
6
3
4
2
1 2
0 0
0 1 2 3 4 0 2 4 6
Fig. 3 Representation of estimated versus calculated lengths of (a) 150, (b) 200, (c) 250,
(d) 300, (e) 350, and (f) 400 mm diameter sewers
of sewers, respectively, for estimating the expenditure on sewerage network in GRB

based on discussions with practicing engineers and representatives of several con-
sulting firms involved in turnkey projects on sewerage systems such as Tata
Consulting Engineers, AECOM, etc.
a 8 b 10
8
6
Estimated, km
Estimated, km
6
4
4
2
2
0 0
0 2 4 0 2 4 6
c 12 d 8
10
6
Estimated, km
Estimated, km
8
6 4
4
2
2
0 0
0 2 4 6 8 0 2 4
e 7 f 9
6
Estimated, km
Estimated, km
5
6
4
3
3
2
1
0 0
0 1 2 3 4 5 0 3 6
Cost of Sewage Pumping
A typical pattern of distribution of estimated expenditure on sewage pumping is

presented in Figs. 9, 10, and 11.
a 12 b 9
10
Estimated, km
Estimated, km
8 6
6
4
3
2
0
0 2 4 6 8 0
Calculated, km 0 3 6
Calculated, km
c 14 d 10
12
8
Estimated, km
Estimated, km
10
8 6
6 4
4
2
2
0 0
0 2 4 6 8 10 0 2 4 6
e 10 f 16
8
12
Estimated, km
Estimated, km
6
8
4
4
2
0 0
0 2 4 6 0 4 8 12
150 mm
200 mm
8% 250 mm 11%
300 mm
350 mm
400 mm
450 mm
500 mm
600 mm
700 mm
750 mm
62% 800 mm 60%
900 mm
1000 mm
1100 mm
1200 mm
1400 mm
Modelled 1600 mm Actual
Fig. 6 Comparison of the estimated and actual percentage distribution of lengths of various
diameter sewers for a typical Class I town
It may be noted that in sewage pumping, the major expenditure is on operation

and maintenance (almost 85–90%) in which 90% is on energy consumption. In the
capital expenditure, the major expenditure (almost 85–90%) is on procurement of
pumps.
Cost of Sewage Treatment
The cost of treating sewage is estimated with the consideration that sewage would be
converted into water that could be recommended for use for all domestic, commer-
cial, industrial, horticultural, and agricultural purposes except for direct human
contact such as drinking, bathing, etc. This is based on the extensive studies
conducted by Consortium of seven IITs for preparing GRBMP. For ballpark esti-
mates of such kind of treatment, a standard chain of treatment processes involving
activated sludge process at the secondary level and coagulation-flocculation
followed by rapid sand filtration and disinfection using chlorination at the tertiary
level is considered. It is to be noted that this does not imply that other equivalent
treatment processes are not acceptable. It is to arrive at the most reasonable and
conservative estimates for planning processes that such a treatment chain is consid-
ered in this study.
The Capex and annual Opex for such treatment have been worked out as INR
11 and 1.4 million per MLD, respectively (Table 1). Considering 30 years of
operation and maintenance (Opex) cost and discounting at 12% per year, a typical
net present value (NPV) of expenditure on sewage treatment is estimated at INR
22.34 million/MLD. A typical breakup of Capex and Opex on sewage treatment is
presented in Fig. 12.
20
Table 3 Typical estimated percentage contributions of various items in unit cost of laying sewers of different diameters
Sewer diameter, mm
Item 150 200 250 300 350 400 450 500 600 700 750 >750 Weighted average
MSa 5.3 4.9 4.5 4.0 3.2 2.9 2.5 2.1 1.6 1.3 1.1 0.6 3.2
Excavation 2.2 4.0 6.5 9.0 10.9 15.5 19.3 23.9 29.2 34.0 36.7 47.7 19.1
Timbering 23.5 24.3 25.2 24.4 21.8 21.5 19.4 18.0 15.3 13.1 12.3 9.0 19.0
Pipe Cost 7.1 8.2 8.5 11.0 19.5 19.3 18.6 16.8 18.5 17.6 17.3 20.4 13.2
Laying 3.6 4.9 4.5 6.6 7.5 6.8 7.4 7.0 5.8 5.5 5.3 6.1 5.4
Sand filling 0.6 0.5 0.5 0.4 0.3 0.3 0.3 0.2 0.2 0.1 0.1 0.1 0.3
Dewatering 2.3 2.1 1.9 1.7 1.4 1.3 1.0 0.9 0.7 0.5 0.5 0.3 1.4
CWb 2.1 2.6 3.0 3.2 3.0 3.1 2.9 2.8 2.5 2.4 2.3 1.6 2.4
Manholes 53.3 48.6 45.3 39.7 32.3 29.3 28.6 28.2 26.3 25.4 24.5 14.3 36.0
a
Material supply
b
Concrete work
S. Shukla and V. Tare
Esmated Cost, INR/m

30000
25000 24500
20000
13300
15000 11800
9500
10000 6100 7100
4600 5100 4600
2800 3100 3300 3800
5000
0
er ted
e
Av igh
ag
e
W
Sewer Diameter, mm
Fig. 7 Typical variation in unit cost of laying sewer of various diameters
Fig. 8 Typical breakup of

estimated capital expenditure
(Capex) on sewerage network
15%
50%
35%
Pipes Other Expenditures

Manholes (Labors, Materials etc.)

2%
estimated capital expenditure 9%
on sewage pumping stations
Pump
Material Supply
Construction Cost
89%

operation and maintenance 9%
expenditure on sewage
pumping stations
Power Cost
Materials
(Labours etc.)
91%
Fig. 11 Typical distribution

of estimated annualized
capital (Capex) and operation 13%
and maintenance (Opex)
expenditure on sewage
pumping Capex
Opex
87%

capital (Capex) and operation
and maintenance (Opex) 48%
expenditure on sewage 52% Capital
treatment O&M
Cost Estimation of Complete Sewerage System
The entire sewerage system costs can be arrived at by adding the cost of its three
components, namely, sewerage network, sewage pumping, and sewage treatment.
The results are presented in Figs. 13 and 14.
It is important to note that the major share (64%) of the total annual expenditure is
incurred on sewerage network, which is unavoidable if water flush toilets are used
and onsite treatment of sewage is not possible. This is generally the case in most
urban agglomerations. These costs could be substantially reduced if several small

estimated total annual
expenditure among three
components of sewerage 28%
systems
Sewerage Network
Sewage Pumping
64%
8% Sewage Treatment
a b
19%
24%
50%
79% 26%
2%
Sewer Netwok Sewage Pumping Sewage Treatment
Fig. 14 Typical breakup of estimated (a) Capex and (b) Opex expenditure among three compo-
nents of sewerage systems
sewerage networks are planned as this would effectively reduce the total area
covered, while serving the same population as sewerage network cost increases at
a much higher rate with an increase in coverage area than the increase in population.
This can be inferred from the empirical relations developed for estimating lengths of
different diameter sewers (refer to Table 2). For higher-diameter sewers, exponent of
the area is much higher than that for population, and hence contribution of higher-
diameter sewers to the sewerage network costs increases. This supports the case of
decentralized sewerage systems.
Analysis of Opex expenditure on sewerage systems (Fig. 14b) reveals that 26% of
the expenditure is incurred on pumping sewage, which again can be substantially
reduced if the area covered is reduced. It is important to note that out of the 26%
Opex expenditure on sewage pumping, approximately 91% is on energy which
increases the carbon footprint. It is also important to note that out of the total annual
energy consumption on sewerage system, major portion (56%) is on sewage
pumping (Fig. 15). While energy consumption on sewage pumping can be reduced
Fig. 15 Typical distribution

of energy consumption
between sewage treatment and 44%
sewage pumping in Sewage Treatment
56%
centralized sewerage systems
Sewage Pumping
by adopting decentralized sewerage network, energy consumption on sewage treat-

ment is unlikely to change.
Estimated Costs of Provisioning Sewerage Systems in Major

Urban Agglomerations in Ganga River Basin
Based on (i) the results reported in the preceding sections of this chapter and (ii) the
information collated for urban agglomerations in Ganga River Basin (GRB), an
attempt has been made to arrive at ballpark estimates of expenditure on provisioning
sewerage infrastructure. Significant urban agglomerations are considered as Class I
and Class II towns defined on the basis of population (Class I towns, population
100,000; Class II towns, population exceeding 50,000 and less than 100,000).
A summary of the total ballpark estimates of capital expenditures on provisioning
sewerage infrastructure for Class I and Class II towns of each of the GRB states is
presented in Table 4. Provisioning of toilets and connection to the sewerage network are
excluded from these estimates as these are considered as part of housing infrastructure.
For each Class I and Class II towns of GRB, annual expenditure on the capital
investment (Capex) for all three components of sewerage systems has been worked
out by multiplying capital expenditure with capital recovery factor (CRF). The CRF
has been calculated as 0.147 using 12% interest over a 15-year period. Operation and
maintenance (Opex) has also been estimated for each of these towns for all three
components separately using the methodology presented and results described in the
previous section of this chapter.
Estimates given in the aforementioned tables can serve as significant inputs in
preparing GRBMP and formulating a strategy for water supply and sanitation in
Class I and Class II towns of GRB. The figures of annual investments on provision-
ing sewerage systems reported in Tables 4 and 5 may appear to be very high, and the
general perception is that such systems require huge land, consume large amount of
energy, and are very expansive and unaffordable for people in the developing
countries like India. Based on this perception, other sanitation systems such as septic
tanks, soak pits, decentralized wastewater systems using anaerobic baffled reactors
followed by root zone treatment, bioremediation techniques, etc. are being advo-
cated (Bartram and Cairncross 2010). These are perceived to be low-energy con-
suming and low-cost technologies. In order to get more clarity and facilitate in
making rational decision than taking decisions based on perceptions, estimates on
1
Table 4 Estimated capital expenditure on sewerage infrastructure in Class I and Class II towns of NRGB
Estimated capital expenditure, millions of
INR
S Population in Estimated sewage Sewerage Sewage Sewage Estimated total capital expenditure,
No. State millions generation, MLD network pumping treatment millions of INR
01 Uttarakhand 2.333 252.0 10392.4 97.1 2772.3 13261.8
02 Uttar 32.722 3534.1 163797.7 2573.2 38874.3 205245.2
Pradesh
03 Himachal
Pradesh No Class I or II towns
04 Haryana 5.481 591.9 34765.5 388.0 6511.0 41664.5
05 Delhi 14.344 1549.2 45491.4 2064.6 17040.4 64596.4
06 Rajasthan 7.976 861.4 63009.1 1022.1 9475.4 73506.6
07 Madhya 12.588 1359.4 77257.1 1070.2 14954.5 93281.8
Pradesh
08 Bihar 8.391 906.2 45724.4 405.0 9967.8 56097.2
09 Chhattisgarh 3.586 387.3 30470.0 293.2 4259.9 35023.1
10 Jharkhand 6.037 652.0 37615.7 364.0 7171.9 45151.6
11 West Bengal 18.124 1957.4 90572.9 1078.5 21531.0 113182.4
Assessment of Some Aspects of Provisioning Sewerage Systems: A Case. . .
Total 111.582 12050.9 599096.2 9355.9 132558.5 741010.6

25
26
Table 5 Estimated annual expenditure on sewerage infrastructure in Class I and Class II towns of NRGB
Estimated annual expenditure, millions of INR
S Population in Estimated sewage Sewerage network Sewage pumping Sewage treatment Total
No. State millions generation, MLD Capex Opex Capex Opex Capex Opex Capex Opex
01 Uttarakhand 1223.2 136.5 1527.7 155.9 14.3 91.2 407.5 354.8 1949.5 601.9
02 Uttar 19206.5 2143.5 24078.3 2456.9 378.4 2415.6 5714.5 4975.8 30171.2 9848.3
Pradesh
03 Himachal
Pradesh No Class I or II town
04 Haryana 5.481 570.0 5110.5 521.5 57 364.3 957.1 833.4 6124.6 1719.2
05 Delhi 14.344 1491.7 6687.3 682.4 303.5 1937.7 2504.9 2181.1 9495.7 4801.2
06 Rajasthan 7.976 829.5 9262.3 945.1 150.2 959.1 1392.9 1212.8 10805.4 3117
07 Madhya 12.588 1309.1 11356.8 1158.8 157.3 1004.7 2198.3 1914.1 13712.4 4077.6
Pradesh
08 Bihar 8.391 872.6 6721.5 685.8 59.6 380.3 1465.3 1275.9 8246.4 2342
09 Chhattisgarh 3.586 372.9 4479.1 457.1 43.1 275.2 626.2 545.3 5148.4 1277.6
10 Jharkhand 6.037 627.8 5529.5 564.2 53.5 341.6 1054.3 918 6637.3 1823.8
11 West Bengal 18.124 1884.9 13314.2 1358.6 158.6 1012.3 3165 2756 16637.8 5126.9
Total 111.582 11604.3 88067.2 8986.3 1375.5 8782 19,486 16967.2 108928.7 34735.5
(i) footprint for sewage treatment, (ii) energy consumption, and (iii) per capita daily
expenditure on availing the benefits of sewerage infrastructure have been worked
out. Footprint for sewerage networks has been excluded as they are underground and
do not require separate space. Footprint for sewage pumping is much smaller and
negligible compared to the footprint for sewage treatment.
However, energy consumption for both sewage pumping and sewage treatment has
been considered. Tables 6 and 7 present a summary of such results for all Class I and
Class II towns belonging to 11 different Indian states and that are part of the GRB.
It is interesting to note that the footprint for sewage treatment is approximately 0.1 m2
per person which is one tenth of the size of the toilet. The energy consumption in sewage
pumping and treatment ranges from 0.03 to 0.1 KW-h which is equivalent to lighting
30 to 100 watt bulb for 1 h. The total per capita expenditure in availing sewerage
infrastructure is estimated to be in the range of INR 1.8–10.8 with an average of INR
3.93 and standard deviation 1.4. The higher values correspond to towns with very low
population density, and the lower values correspond to very high population densities.
The sewerage network and sewage pumping cost increase with a decrease in population
density. In cases where habitations are separated by major roads, streams, water bodies,
parks, playgrounds, open fields, large commercial establishments, etc., it may be much
meaningful to plan for decentralized sewerage treatment systems by dividing the town
into number of zones with separate sewerage system for each zone. This may reduce
both energy consumption and total per capita expenditure. It is interesting to note from
some of the recent studies (Luthra 2013) that expenditure on some of the perceived to be
low-cost alternative sanitation systems is also in the same range with much lower quality
and substantial adverse impacts on environment.
Benefits of Provisioning Sewerage Systems
Provisioning of sewerage systems has many tangible and intangible benefits. The
intangible benefits include aesthetically improved towns, much less exposure to
infectious diseases thereby substantial savings in expenditure on health, less suffer-
ing and higher quality time available for meaningful activities, etc. Some of the
tangible benefits include unpolluted water bodies and more water of better quality
available for many functions including ecological. Here, an attempt has been made
to quantify availability of good quality water through treatment of sewage up to the
tertiary level and compare it with present-day dry weather flows (November through
May) at some select locations on some select rivers in the Ganga Basin. Select
locations are some of the flow-monitoring sites of the Central Water Commission
(CWC), Ministry of Water Resources (MoWR), GoI. The sites are shown in the map
of Indian part of GRB (Fig. 16). The map also shows some Class I and Class II towns
immediate upstream of the monitoring sites whose treated or untreated sewage,
directly or indirectly, likely to contribute to the river flows. Comparison of the
90% dependable dry weather flows with the treated water available from sewage
of the Class I and Class II towns located immediately upstream of the selected CWC
monitoring sites is presented in Table 8.
28
Table 6 Estimated footprint, energy consumption, and expenditure on sewerage infrastructure in Class I towns of NRGB
Estimated annual Estimated per capita per day
Estimated STP Estimated Energy Expenditure on Energy
Number land required energy consumption sewerage system consumption in
S of Class Population per capita in demand in in gigawatt- in millions of KW-h (unit of Expenditure
No. State I towns in millions m2 megawatts hour INR electricity) in INR
01 Uttarakhand 8 2.121 0.1 51.0 0.087 2257.3 0.03–0.05 2.2–4.4
02 Uttar 62 29.613 0.1 755.0 1.735 36074.9 0.03–0.09 2.3–5.5
Pradesh
03 Himachal
Pradesh No Class I town
04 Haryana 16 5.317 0.1 133.3 0.284 7630.2 0.03–0.08 2.5–5.8
05 Delhi 15 13.482 0.1 376.5 1.183 13541.0 0.03–0.10 1.8–6.2
06 Rajasthan 19 7.689 0.1 209.0 0.606 13388.3 0.04–0.11 3.2–8.0
07 Madhya 27 11.934 0.1 305.9 0.719 16829.5 0.03–0.09 1.8–10.8
Pradesh
08 Bihar 28 6.929 0.1 168.8 0.312 8473.0 0.03–0.06 2.5–5.5
09 Chhattisgarh 9 3.138 0.1 80.0 0.184 5252.7 0.03–0.08 3.3–7.3
10 Jharkhand 15 4.801 0.1 119.4 0.246 6474.8 0.03–0.07 2.0–6.5
11 West Bengal 62 17.124 0.1 422.4 0.834 20184.6 0.03–0.07 1.3–7.2
Total/range 261 102.148 2621.3 6.190 130106.3 0.03–0.11 1.3–10.8
1
Table 7 Estimated footprint, energy consumption, and expenditure on sewerage infrastructure in Class II towns of NRGB
Estimated annual Estimated per capita per day
Estimated STP Estimated Energy Expenditure on Energy
Number land required energy consumption sewerage system consumption in
S of Class Population per capita in demand in in gigawatt- in millions of KW-h (unit of Expenditure
No. State II towns in millions m2 megawatts hour INR electricity) in INR
01 Uttarakhand 4 0.212 0.1 5.0 0.007 294.2 0.03–0.04 2.2–6.6
02 Uttar 43 3.109 0.1 72.7 0.104 3944.7 0.03–0.05 1.8–8.6
Pradesh
03 Himachal
Pradesh No Class II town
04 Haryana 3 0.164 0.1 3.8 0.005 213.6 0.03–0.03 3.3–3.9
05 Delhi 14 0.862 0.1 19.8 0.024 755.9 0.03–0.04 1.8–4.5
06 Rajasthan 4 0.287 0.1 6.9 0.011 534.3 0.04–0.04 4.2–5.9
07 Madhya 10 0.654 0.1 15.4 0.023 960.6 0.03–0.04 2.9–5.2
Pradesh
08 Bihar 23 1.462 0.1 34.3 0.051 2115.5 0.03–0.04 2.6–6.6
09 Chhattisgarh 6 0.448 0.1 11.1 0.022 1173.1 0.04–0.07 4.8–10.7
10 Jharkhand 17 1.236 0.1 29.3 0.046 1986.3 0.03–0.05 2.8–7.0
11 West Bengal 15 1.000 0.1 23.6 0.036 1580.2 0.03–0.04 2.7–6.4
Total/range 139 9.433 221.9 0.329 13558.4 0.03–0.07 1.8–10.7

29
Himachal Pradesh
Uttarakhand
Delhi
Haryana
Uttar Pradesh
Rajasthan Bihar
Madhya Pradesh Jharkhand

Chhatisgarh
West Bengal
CWC Station
Towns draining sewage in Yamuna Yamuna River
Towns draining sewage in Ganga Ganga River
Towns draining sewage in Ramganga Ramganga River
Towns draining sewage in Betwa Betwa River
Towns draining sewage in Gomati Gomati River
Towns draining sewage in Chambal Chambal River
Towns draining sewage in Kshipra Kshipra River
Towns draining sewage in Ken Ken River
Fig. 16 Schematic representation of GRB showing a few rivers of the basin and Class I and Class
II towns in the immediate upstream of selected flow-measuring sites of CWC
The data presented in Table 8 reveals that contribution of treated sewage in

comparison with dry weather flows is very high at many places. The quantities of
treated sewage are estimated as 70% of the sewage generated. In other words,
approximately 56% of water supply can be supplemented and saved by recycling
treated sewage. It may be noted that in many locations/stretches of the rivers,
1
Table 8 Comparison of dry weather flow with estimated available water from treated sewage at select locations in Ganga River Basin
CWC monitoring station Dry weather (November Estimated available Percent of dry
Nearby 1–May 31) 90% dependable water from treated weather flow,
River Name Latitude, N Longitude, E town flow, m3/s sewage, m3/s %
Yamuna Delhi 28 390 43.9500 77 140 44.8800 Delhi 16.24 1.24 7.64
Railway
Bridge
Yamuna Mathura 27 300 04.8800 77 410 45.7300 Delhi 14.24 12.61 88.55
Yamuna Mathura 27 300 04.8800 77 410 45.7300 Mathura 14.24 7.26 50.98
Yamuna Agra 27 150 26.4700 78 10 24.5200 Agra 11.27 6.86 60.87
Poiya
Ghat
Yamuna Etawah 26 440 41.9600 78 590 19.4600 Etawah 12.20 2.17 17.79
Yamuna Pratappur 25 210 27.7800 81 400 52.8200 Allahabad 147.95 0.33 0.22
Kshipra Ujjain 23 100 10.5700 75 460 15.6100 Ujjain 0.00 2.72 –
Betwa Basoda 23 540 04.9900 77 550 19.8000 Basoda 0.00 2.74 –
Chambal Mandwara 25 230 04.5900 76 090 07.6400 Kota 0.72 0.88 122.22
Chambal Dholpur 26 390 16.7900 77 530 45.3300 Dholpur 8.75 0.11 1.26
Gomti Lucknow 26 520 05.8900 80 550 31.3000 Lucknow 9.55 2.95 30.89
Ramganga Bareilly 28 160 32.0000 79 220 40.0000 Bareilly 17.18 2.87 16.71
Ganga Fatehgarh 27 240 00.0000 79 370 00.0000 Farrukhabad 15.15 2.74 18.09
Ganga Ankinghat 26 550 00.0000 80 050 00.0000 Kanpur 69.94 0.64 0.92
Ganga Bhitaura 26 020 13.6500 80 490 57.5000 Allahabad 96.97 1.98 2.04
31
the entire dry weather flow could be due to sewage. It is also important to note that at
very few locations or stretches of the river, the dry weather flows exceed ten times the
estimated treated sewage flows, which is generally assumed while setting the effluent
discharge standards. In reality the situation at most locations/stretches is inferior to
what is presented here due to cumulative effect. Thus, looking at the comparison of
the estimated sewage generation and dry weather flows, it can be inferred that
treatment of sewage up to the tertiary level or equivalent is essential if river water
quality standards befitting the ecological needs are to be maintained. It is thus
necessary to consider sewage as a significant source of water for both human and
ecological needs and bring in the concept of a much higher level (at least tertiary level)
of treatment for Class I and Class II towns in the GRB. The cost of provisioning
sewerage systems does not appear to be unaffordable on per capita per day basis
considering the benefits and savings in water supply and health-related expenditures.
Discussion
The following conclusions may be drawn based on the synthesis of the information
available in the literature and the results presented in this thesis.
• Length of the sewers of various sizes up to 750 mm diameter appears to be

strongly correlated with the population served and area covered by the sewer
network.
• Empirical relations developed from the data gathered from various sources on
sewerage networks for various urban agglomerations in India can be very useful
in estimating the lengths of the sewers of various primary, lateral, and branch
sewers up to 750 mm diameter.
• Approximately 70% of the total length of sewers is comprised of 150 and 200 mm
diameter sewers in typical Indian urban agglomerations.
• Approximately 15%, 35%, and 50% of total capital expenditure on sewerage
network are incurred on sewer pipes, manholes, and laying (including excavation,
timbering, dewatering, bedding, etc.), respectively.
• About 85–90% of annual expenditure on sewage pumping is toward energy
consumption, and about 90% of the capital expenditure on sewage pumping
stations is required for procurement of pumps.
• Typical breakup of total annual expenditure on sewage treatment between Capex
and Opex is 52% and 48%, respectively.
• About 79%, 2%, and 19% of the total capital expenditure on sewerage system are
toward sewer network, sewage pumping, and sewage treatment, respectively,
while about 24%, 26%, and 50% of the total Opex expenditure are incurred in
sewer network, sewage pumping, and sewage treatment.
• Approximately 68%, 8%, and 28% of the total annual expenditure on sewerage
system are incurred on sewerage network, sewage pumping, and sewage treat-
ment, respectively, in a typical Indian town.
• Approximately 56% of the energy bill is toward sewage pumping, while only
44% of energy expenditure is incurred on sewage treatment.
• Total annual Capex and Opex for provisioning sewerage systems in all Class I and
Class II towns of GRB are expected to be INR 1,08,930 and 34,740 million,
respectively. This amounts to the average per capita per day expenditure of INR 3.93.
• The average per capita per day energy consumption in availing sewerage systems
is approximately equivalent to lighting a 40 watt bulb for 1 h.
• The expenditure on sewerage expenditure may be justified in GRB based on
tangible and intangible benefits.
Conclusion
In a developing country like India, budget allocation becomes a very critical

exercise, both for infrastructure development and as a political issue. In general,
water and wastewater are considered dirt and not as resource; however, most of the
countries have started moving toward achieving the Millennium Development Goal
(WHO 2004) of becoming open defecation free, and by adequately treating waste-
water and reusing it instead of dumping the untreated or partially treated wastewater
to sully the environment, urban wastewater treatment can recover the value of water
as a “resource.” However, costs and benefits of such strategies need to be delineated
in quantitative terms to convince the policy makers. However, the availability of
budget for developing comprehensive sewerage infrastructure is a constraint for all
such developing countries. The present study aims to fulfill this gap and provide a
techno-economic framework which helps in preparing the ballpark estimates for
such an infrastructure and the tangible and intangible benefits that would accrue. The
per capita expenditure on providing comprehensive sewerage infrastructure up to the
tertiary treatment shows that expenditure on alternative low-cost sanitation systems
is in the same range. For successful implementation of such a framework, resource
recovery is an important aspect and addressed within the chapter. Individuals and
firms willing to adapt any of the methodologies outlined here are welcome to do so
and are most cordially invited to contact the author to explore options for sharing
data, materials, and expertise.
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Economic Assessment of Provisioning a
Comprehensive Solid Waste Management 2
System: A Case Study of Urban
Agglomerations in Ganga River Basin
Smriti Gupta, Saurabh Shukla, and Vinod Tare
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Cost Estimates of Solid Waste Management Systems: Conventional Approach . . . . . . . . . . . . . . . 38
Collection of Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Cost Estimation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Cost Estimates of Solid Waste Management Systems: Other Approaches . . . . . . . . . . . . . . . . . . . . . . 40
Waste Collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Waste Conveyance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Waste Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Estimation of Capex and Opex of Waste Collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Estimation of Capex and Opex for Waste Conveyance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Estimation of Capex and Opex of Solid Waste Processing Plant . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Findings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Collection of Solid Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Conveyance of Solid Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Treatment of Solid Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Comprehensive Solid Waste Management System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Estimated Costs of Provisioning Solid Waste Management in Major Urban
Agglomerations in Ganga River Basin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
S. Gupta · S. Shukla (*)

e-mail: smritiguptasg@gmail.com; saurabh.shukla2020@gmail.com
V. Tare
Department of Civil Engineering, IIT Kanpur, Kanpur, India
e-mail: vinod@iitk.ac.in

https://doi.org/10.1007/978-3-319-73645-7_4
36 S. Gupta et al.
Abstract
An appropriate techno-economic framework is an essential requirement to
provide solutions for comprehensive solid waste management in urban centers.
The first and foremost step toward it is to have an assessment of having the
management plan in economic sense. Dumping the solid waste as landfills may
appear to be a very low-cost solution and may have certain advantages in
low-lying areas, but it has very serious effects on land, agriculture, underground
water, and surface water bodies as well.
The present chapter aims at estimating the per capita expenditure on solid
waste management with provision of segregation of the total solid waste gener-
ated, proper collection and conveyance of waste and subsequent recycling, and
treatment of different types of wastes. Results indicate that footprint for waste
treatment is approximately 0.7 m2 per person. The electrical energy consumption
in complete solid waste management comes out to be 0.001 kilowatt-hour
(KW-h) per person per day, while the equivalent energy in the form of fuel
consumption is 0.017 KW-h per person per day for Class I towns, and subsequent
value for Class II towns is 0.016 KW-h per person per day. The total per capita
expenditure for having complete solid waste management system is estimated to
be INR 1.15 per capita per day. The cost of provisioning solid waste management
systems does not appear to be unaffordable on per capita per day basis consid-
ering the benefits and savings in ensuring good quality of agricultural land
availability, no groundwater or surface water hazards and, hence, minimum health
hazards.
Keywords
Solid waste management systems · Waste collection · Waste conveyance · Waste
treatment · Cost estimates · Minimum landfill · Waste segregation · Capex ·
Opex · Ganga River Basin · Ganga River Basin Management Plan
Introduction
Solid waste is a major nonpoint source of pollution which adversely affects land,
groundwater, and surface water bodies if not managed and treated properly (Lella
et al. 2017). Among the three types of solid waste, namely, municipal, industrial, and
biomedical waste, municipal waste is a major concern because of its large quantity
(Sharholy et al. 2008).
Government of India asked the consortium of seven IITs (Indian Institute of
Technology) to prepare Ganga River Basin Management Plan (GRBMP). One of the
most important challenges/vision of the consortium was to prepare an action plan for
“Unpolluted Flow” or “Nirmal Dhara” in all rivers of the Ganga Basin. To achieve this
objective of proper sanitation in towns of our country, an effective and efficient solid
waste management is needed. The main approach to achieve the ultimate objective of
2 Economic Assessment of Provisioning a Comprehensive Solid Waste. . . 37
“Nirmal Dhara” has been to identify the type of polluting wastes, their sources of
generation (point and nonpoint sources), and the techno-economic feasibility of
collecting and treating them for their safe environmental discharge and/or possible
recycle or reuse. Figure 1 illustrates the main identification results and the tasks.
In consideration of the magnitudes of municipal solid waste generation from
different urban locales, urban settlements are divided into Class I towns (having
population over 100,000) and Class II towns (having population between 50,000 and
100,000) (RBI 2003). The following steps concerning solid waste management are
considered essential:
1. All solid wastes generated in Class I and Class II towns of Ganga River Basin
(GRB) need to be collected and transported efficiently ensuring proper hygiene
and sanitation.
2. Segregation of the collected waste.
3. Suitable treatment or disposal methods should be meted out to different types of
waste.
4. Minimum landfill concept needs to be ensured to prevent environmental hazards.
5. Recycling of optimum amount of recyclable or reusable waste is the need of
the hour.
The above measures are essential to overcome the declining state of urban solid
waste management in GRB. An appropriate techno-commercial framework needs to
be developed for sustainable solid waste management system for the urban centers.
Fig. 1 Types and sources of wastes and main identification tasks (IIT GRB 2013)
38 S. Gupta et al.
A lot can be achieved if solid waste is considered as a “resource recovery” option

and not just as waste. Adequate disposal strategy with minimal landfill and recycling
as an integral part will provide an effective management of such huge amount of
waste being generated in towns and cities of the country (Narayana 2009). The
present study was thus initiated to persuade the policy makers and make them
understand the costs and benefits in quantitative terms.
Firstly, it is important to have an appropriate ballpark estimate of expenditure on
provisioning solid waste management systems, and the tangible and intangible
benefits that would accrue as solid waste management can be considered as one of
the major activities which a municipality undertakes.
A complete solid waste management system includes waste collection, waste
conveyance, and waste treatment. A recent study by Central Pollution Control Board
(CPCB) has estimated that in 299 Class I cities in India, manual collection of solid
waste comprises of 50%, while waste collection using trucks comprises only 49%
(CPCB 2000a). Further India is facing challenges for efficient waste conveyance and
treatment as well. Waste littering all over the place is not only aesthetically unpleas-
ant but also affects public health, agricultural land, groundwater, and surface water
(Hazra and Goel 2009). Hence to address these burning issues, it is necessary to have
an estimate of expenditure on having complete infrastructure for solid waste man-
agement for full coverage of urban agglomerations in the country, in general, and
Ganga River Basin (GRB) in particular.
Cost Estimates of Solid Waste Management Systems:

Conventional Approach
The Manual on Municipal Solid Waste Management by Central Public Health

and Environmental Engineering Organisation (CPHEEO), Ministry of Urban
Development (CPHEEO 2000), briefly mentions following about planning and
arriving at the cost of solid waste management projects.
(a) Capital expenditure shall include all the costs such as civil construction, material
supply and erection costs, land acquisition costs, engineering design and super-
vision charges, and interest charge on loan.
(b) Operation and maintenance cost, after the project is started, shall consider
amortization and interest charges on capital borrowing, expenditure made on
staff, chemicals, energy, transport, repair work, all the equipment/tools, insur-
ance, and overheads.
The planning for such projects starts generally with a preliminary study to provide
guidelines for suitable methods to be adopted. These studies are then used for the
preparation of City Master Plan (CMP) and Detailed Project Report (DPR) for a
particular town. Ideally CMPs should form the base for solid waste management
systems. Currently only few towns have CMPs, and most of these are based on
inadequate data and information.
Collection of Information
Conventionally, for preparing an estimated expenditure on comprehensive solid

waste management systems, all the basic information is required to be collected.
Some of the essential information/data includes, but not restricted to:
(a) Population and number of households of the town

(b) Per capita per day waste generation of that town
(c) Identification of types of waste to be collected
(d) Deciding the criteria for sweepers and equipment to be used
(e) City Master Plan, long-term comprehensive development plans for cities and
towns, urban planning, city planning area, urbanization zone and urbanization
control area, land use plan, road plan, urban development as rezoning, residen-
tial estates and industrial complexes, etc.
(f) Possible locations for composting site, sanitary landfill site, site for setting up
transfer stations, and sorting-cum-treatment plant
(g) Traffic and land use patterns of the city
(h) Details of the roads like length, width, and conditions to ensure proper and
efficient conveyance
(i) Assessment of present coverage and future expansion possibilities
(j) Preparation of service area maps and other relevant documents
After collection of aforementioned information, several other reports like feasi-

bility reports, pre-feasibility reports, and identification reports are to be made. This
generally ends with preparation of DPR which also looks at the salient features of
financial and administrative aspects.
Cost Estimation
There are no detailed methods provided for cost estimation in the manual on solid
waste (CPHEEO 2000), but, to arrive at the total annual fund requirements for the
project execution, DPRs recommend that cost estimation of all the components of the
project is prepared, and thus annual requirement of funds for each year is worked out
making due allowance for physical contingencies and annual inflation. Further it is
required to prepare recurring annual costs of the project for the next few years (say
10 years) covering operation and maintenance expenditure for the entire system (staff,
chemicals, energy, spare parts and other materials for system operation, transportation,
etc.). The cost estimates are prepared considering the following points:
(a) Outlining the basic assumptions made for unit prices, physical contingencies,
price contingencies, and escalation
(b) Summarizing the estimated cost of each component for each year till its
completion and working out total annual costs to know annual cash flow
requirements
40 S. Gupta et al.
(c) Estimation of foreign exchange cost if required to be incurred

(d) Working out per capita cost of the project on the basis of design population and
cost per tonne of the waste collected, conveyed, and treated and comparing these
with the government norms, if any
Once the estimation of cost of solid waste management systems is done, the need
for an institutional and financial plan rises which needs the identification of respon-
sible and capable organization which can be trusted for the completion of the project
and also the identification of all sources of funds for implementation of the project,
indicating year-by-year requirements from these sources, to meet expenditure as
planned for completing the project as per schedule; stating how the interest during
construction period will be paid, or whether it will be capitalized and will be paid in
loan; and explaining the procedures involved in obtaining funds from the various
sources.
Cost Estimates of Solid Waste Management Systems: Other

Approaches
The conventional approach followed is to follow the DPRs and prepare bill of
quantities (BOQ) for various items and use unit costs to get the total expenditure.
However, this approach requires availability of detailed design and specifications
which in most cases are not available and preparation of DPRs and BOQs are not
possible at the planning stage.
Waste Collection
Collection of solid waste requires huge manpower in form of sweepers, cart workers,
drivers, etc. and also small vehicles like mini-waste collectors to collect the waste
from different localities (Jaunich et al. 2016). In order to have cost estimates, the first
step is to evaluate the number of workers (sweepers, pushcart workers, etc.), number
and type of vehicles, and other equipment like brooms, bins, etc. Generally, the unit
costs can be easily worked out for different settings. However, the other information
is generally not available. Commonly, the operation and maintenance expenditures
on waste collection are taken as the 10% of the capital cost.
Waste Conveyance
Waste conveyance requires large number of vehicles, and thus operation and main-
tenance expenditures are very high (fuel cost, repair, and maintenance of vehicles).
Different types of vehicles can be used for transportation of waste and vary from
city to city. The number of trips to be made and after deciding the location of
transfer station/treatment site, the distance to be traveled and thus incurred fuel
cost is calculated. Generally, the operation and maintenance expenditures on waste

conveyance are taken as 30% of the capital cost.
Table 1 gives a brief idea regarding estimation of distance and cost calculation
in waste conveyance. According to a Guidance note (MoUD 2009), the following
assumptions are taken to calculate the number of vehicles and cost of waste
conveyance along with incurred fuel cost:
(a) Quantum of waste generated/collected (tons per day, TPD): 300

(b) Rejects from composting facility (@35%) (TPD): 105
(c) Vehicle capacity – long haul compactor truck (Metric tons, MT): 12
(d) Average one-way distance to regional facility (km): 40
(e) Maximum number of trips per truck per day: 3
(f) Vehicle speed – including tipping time, stoppages, and halts considered (aver-
age) (km/h): 25
(g) Vehicle mileage (km per liter): 4.5
(h) Cost of vehicle (Rs.): 2,500,000
(i) Maintenance of vehicle (% of capex): 6%
(j) Current diesel price (Rs./liter): 42
(k) Salary of driver (Rs. per month): 8000
(l) Salary of helper (Rs. per month): 5000
Waste Treatment
Estimation of waste treatment costs requires information on treatment technology

adopted, unit costs, and quantity of waste to be treated. In India, use of advanced
treatment technologies is considered impractical and hence generally not practiced.
Use of landfills (mostly unsanitary) is widely used which is not a good option as
such (Srivastava and Ramanathan 2008). The next commonly used process is
composting. The cost of these components is done by identifying the unit costs of
all the items and cost of land acquisition for the same.
Generally, the operation and maintenance expenditures on waste conveyance are
taken as the 20% of the capital cost.
The conventional solid waste management systems call for segregation of solid
waste at source only, but this is not widely practiced, and hence the cost of
segregation of solid waste is not available, which calls for proposing the strategies
for waste segregation at either source or treatment plant.
The conventional approach for estimation of expenditure on provisioning solid
waste management systems calls for detailed specifications of waste collection
network, waste conveyance, and waste treatment plants. The required information
to get a ballpark estimate is often not available at the planning stage. This creates the
requirement of having a suitable approach for ballpark estimates of solid waste
management systems at the planning stage which does not depend on the detailed
specifications. Essentially not much published literature is available on such
42
Table 1 Cost estimate for transportation of rejects for the distances varying from 40 to 70 km
Waste quantity
(TPD) 10 20 40 75
One-way travel
distance
(between source
and disposal
site) in km 40 50 60 70 40 50 60 70 40 50 60 70 40 50 60 70
C and T cost
Capex 0.18 0.18 0.18 0.18 0.18 0.36 0.36 0.54 0.36 0.54 0.54 1.08 0.72 1.08 1.08 1.98
(Rs. crore)
Unit capex (Rs./ 49.32 49.32 49.32 49.32 24.66 49.32 49.32 73.97 24.66 36.99 36.99 73.97 26.30 39.45 39.45 135.62
tonne)
O and M Cost 8.74 10.10 11.42 14.57 11.42 15.24 17.30 21.10 21.29 27.12 31.20 40.58 38.33 49.32 56.71 73.11
(Rs. lakh)
Unit O and M 239.4 276.7 312.9 399.2 156.4 208.8 237.0 289.0 145.8 185.8 213.7 277.9 140.0 180.2 207.2 267.1
cost for
transport (Rs./
tonne)
*While this is an illustration of the argument, it is recommended that every ULB undertake an estimation of costs in its specific context to arrive at a financially
viable distance for transporting waste (MoUD 2009)
S. Gupta et al.
approaches and not much information could be obtained through practicing

engineers, professionals, and consulting organization. It is reasonable to develop
approaches based on information available on solid waste management systems in
India and worldwide, for ballpark estimates of solid waste management systems with
some reasonable assumptions.
State of solid waste management infrastructure in India in general and in Ganga
River Basin in particular is extremely poor. Even though the adequate resources
required to develop such infrastructure are mostly available, lack of awareness, bad
habits of littering around, poor planning, and improper and unscientific treatment
lead to a mess, and the waste generation is increasing at a rapid rate. The day is not
very faraway when all open lands in urban centers will become dumping grounds.
The Ministry of Environment and Forest (MoEF) created a framework in 2000,
with the introduction of MSW (Management and Handling) Rules, under the
Environment Protection Act, 1986, that entrusted the urban local bodies with the
responsibility of managing MSW. But in most of the towns, these guidelines are not
followed efficiently, and most of the MSWM budget is spent only on collection of
the waste. Further lack of systematic execution and maintenance of the equipment
decreases the collection efficiency after some time. As a result, not much benefit has
been seen and no viable model is in the sight. It is very vital that an appropriate
techno-commercial framework is developed for sustainable solid waste management
system for the urban centers.
Solid waste management requires proper infrastructure, which is becoming
complex due to the unplanned growth of urban centers, and this is why the first
and foremost prerequisite is to have an assessment of provisioning solid waste
management system in economic sense. This necessity has been the genesis of the
present study. Provisioning of solid waste management systems yields certain
benefits depending upon the choice of technologies and components, their designs,
and efforts and investments made. Complete and efficient collection of solid waste
and treatment of waste in a scientific manner so that most of the waste could be
recycled and/or reused should be done. Further, the approach toward the goal of
“minimum landfill” instead of disposal in open lands and water bodies of urban
agglomerations in the basin should be given a boost.
This study aims at estimating the financial requirements for provisioning of solid
waste management system in all Class I and Class II towns of the Ganga River Basin
(GRB) with the objectives of recycle/reuse of the waste along with “minimum
landfill.” The following specific objectives are set for this study to achieve this goal.
1. Develop suitable methodology for obtaining ballpark estimates for efficient and
complete waste collection in Class I and Class II towns of GRB.
2. Develop suitable framework for obtaining ballpark estimates for waste convey-
ance and waste treatment while promoting waste recycle/reuse.
3. Obtain ballpark estimates of capital investments for having proper infrastructure
for solid waste management and annualized expenditure toward capital (capex)
and sustainable operation and maintenance (opex) of such infrastructure in all
Class I and Class II towns of GRB.
44 S. Gupta et al.
4. Assess financial implications of provisioning sustainable solid waste manage-

ment infrastructure on individuals residing in the urban agglomerations of GRB.
5. Approach toward the goal of “minimum landfill” and encourage sorting of waste
at source.
The scope of the study is limited to availability of secondary information in DPRs

and other such reports on strategies for solid waste management.
Methodology
Solid waste management system includes (i) waste collection, (ii) waste conveyance,
and (iii) waste treatment. Estimation of capital (capex) and operation and mainte-
nance (opex) costs for these three components has been worked out separately for all
Class I and Class II towns in Ganga River Basin (GRB). The following sections
briefly describe the methodology adopted.
Estimation of Capex and Opex of Waste Collection
This involved deciding the layout of the whole collection process, adopting an
appropriate strategy which facilitates proper hygiene of the streets and open spaces
besides ensuring people’s satisfaction and ease to dispose of the waste. Keeping in
mind the above issues, “door-to-door collection” strategy has been proposed which
involves collecting of waste from the households itself by sweepers and pushcart
workers, transferring it from pushcarts into mini-waste collectors which carry it to
some distance, and then eventually transferring the waste into compactors.
The costs for the required components mentioned above were worked out based
on the Manual on Municipal Solid Waste Management – CPHEEO – Ministry of
Urban Development (2000) and Detailed Project Reports (DPRs) of several cities
like Ghaziabad, Kanpur, Vadodara, etc. which were made available by officials of
MoEF (Ministry of Environment and Forests). Population and area of each town of
GRB was taken from a recent study (Shukla 2013). Waste generation is assumed to
be 0.5 kg per capita per day.
The criterion used in estimating the quantities of various items of waste collection
is given in Table 2.
The quantities, thus calculated, were multiplied by rates of each to calculate capex
and opex of the process. To estimate the annual expenditure on waste collection,
“annualized capex” was also calculated for equipment for a loan period of 5 years at
an interest rate of 12%. This was done by multiplying the total capex of all
equipment with a capital recovery factor (CRF) of 0.28.
To determine the expenditure on energy, fuel demand was calculated for the
vehicles. For this purpose, the town area is assumed to be a square, and the distance
to be traveled per day by all vehicles is related to the diagonal of this square. For the
mini-waste collectors, cost of fuel per day is calculated considering mileage of 8 km
Table 2 Criterion/assumptions for different items in waste collection

S No Item Criterion/assumptions
1 Number of sweepers 1 for 200 households + 15% extra
2 Pushcart workers 1 for 2 sweepers
3 Pushcarts 1 for each worker + 25% extra
4 Storage bins (4.5 cum)/dumper placers 1 for 2000 persons + 25% extra
5 Mini-waste collectors 1 for 7 MT/day + 25% extra
6 Manpower (drivers, etc.) 2 for all the carriers + 25% extra
*cum cubic meter, *MT/d metric tons/day
per liter (market research) and taking the distance traveled by each as one-tenth of
the length of the diagonal.
Estimation of Capex and Opex for Waste Conveyance
Waste conveyance involves vehicles for transporting the collected waste to the
sorting-cum-treatment plant and transfer station(s). The conveyance cost is estimated
by summing up the annualized capital cost and operation and maintenance cost in
terms of manpower and energy expenditure on vehicles to be used in waste convey-
ance. The vehicles include compactors, hook lifters, and dumper placer carriers. The
cost also includes the cost of establishment of transfer station, which empirically has
a relation with the capital expenditure and hence is taken as 10% of the total capex,
and then this cost is added to calculate the final capex. Transfer stations will serve as
sites for transferring waste from compactors to hook lifters so as to further transport
it to the sorting-cum-treatment site.
The criterion used in estimating the quantities of various items of waste collection
is given in Table 3.
Annualized capex was computed the same way as described in earlier sections.
Energy expenditure in this case is the sum of fuel consumption by vehicles and electricity
consumption at transfer station. The town area has been assumed as square as was done in
estimating cost of collection. The details of vehicles used are given in Table 4.
Estimation of Capex and Opex of Solid Waste Processing Plant
Estimation of cost of solid waste treatment has been done considering that the waste
is properly segregated and suitable end point solution is provided to each type of
waste. Maximum recycling and minimization of landfill were the twin objectives
while deciding upon the layout of the processing plan.
The total waste collected from a city is conveyed to the sorting-cum-treatment plant
as described in the previous sections. This waste consists of (i) organic or biodegrad-
able waste (60%), (ii) recyclable waste (11%), and (iii) construction waste and drain
silt (29%). While organic matter (leaves, food waste, etc.) needs treatment such as
46 S. Gupta et al.
Table 3 Criterion/assumptions for different items in waste conveyance

S No Item Criterion/assumptions
1 Compactors 1 for 35 MT/day + 25% extra
2 Hook lifters of 20 cum capacity 8 trips a day, each of 15 MT capacity +25% extra
3 Dumper placer carriers 1 for 15 containers + 25% extra
4 Bins of 20 cum capacity 1 for each lifter + 50% extra
5 Manpower (drivers, etc.) 2 for all the carriers +25% extra
*cum Cubic Meter, *MT/d metric tons/day
Table 4 Details/assumptions used for vehicles used in waste conveyance

S No Vehicle Mileage (kmpl) Distance traveled per day
1 Compactors 4 Half the length of diagonal
2 Hook lifters 4 Half the length of diagonal
3 Dumper placer carriers 4 Half the length of diagonal
composting, recyclable waste which includes plastic, metals, glass, and rubber can be
sold, and construction waste can be converted into other usable forms like bricks, tiles,
etc. Segregation of the waste is thus an essential step and needs to be properly planned
out. There are a number of segregation techniques which are being used across the
world such as induction sorting, manual sorting, magnetic separation, trommel sepa-
rators, etc. But in India to make it practical/feasible for all towns, manual sorting, along
with few mechanized equipment, is recommended.
The complete layout of sorting station is shown in Fig. 2.
The waste from the sorting station is put on conveyor belt with workers standing
on either side of the belt. As the waste moves on the belt, workers pick up the
recyclable waste which includes plastic, metal, glass, and rubber. One worker
collects only one type of waste. Quantity of waste that can be picked is worked
out as 5 ton per person per day (McDougall et al. 2007). Sorting station is assumed to
be working for 24 h a day with the total work being done in three shifts per day.
Paper is excluded from handpicked waste. Percentage distribution of handpicked
materials was worked out from the data available in a study by Central Pollution
Control Board (CPCB 2000b), and the details are given in Table 5.
The speed of the belt is controllable and maintained in such a way that each
worker gets sufficient time to recognize and separate out the target material. The
details of the conveyor belt are given in Table 6.
The recyclable portions of the waste are then washed separately in different
drums, to remove the organic matter, after which they are recycled. The specifica-
tions of drums for washing are given in the Table 7. The waste from the conveyor
belt contains dry organic waste, construction waste, and drain silt. This waste is
passed through destoner machines with a capacity of 4 t/h which separate out organic
waste from the sand, silt, and stones which are a part of construction waste.
The details of manpower required at sorting station are given in Table 8.
Water consumption in washing the waste was calculated based on the assumption
that 5 KL water per ton per day is required for this purpose. Waste water generated is
Fig. 2 Layout showing unit operations of sorting station
Table 5 Estimate of Item Content, percent

recyclable (handpicked)
Metals 3
waste
Glass 2
Plastics 4
Rubber/leather 2
Total 11
Table 6 Specifications S No Particulars Specification

of conveyor belt
1 Length of conveyor belt, m 30
2 Speed of conveyor belt, m/h 600
taken as 95% of the water consumed which will be treated up to tertiary treatment so
that the treated water may be recycled and used for washing purpose again. The cost
of treating wastewater containing organics is worked out as INR 17.20 per ton per
day (Shukla 2013).
The organic waste is then taken to the compost plant where it undergoes
decomposition to form compost which can then be used as fertilizer or manure for
48 S. Gupta et al.
Table 7 Equipment Wooden drums (5 t capacity, Running hours per

requirement for washing 2 t/h) Quantity day
of recyclables
Metals 1 15
Glass 1 10
Plastics 1 20
Rubber 1 10
Table 8 Manpower requirement

Manpower Criterion
Labor required for manual picking of recyclable (one worker/5 t)*3 shifts/day + 25%
waste extra
Skilled technicians (device operators, drivers, etc.) 25% of total labor + 25% extra
agricultural purposes. The cost of compost plant is computed by summing up the

cost of equipment, manpower, infrastructure, and other miscellaneous expenses
which include fuel and energy expenditure. The criteria used in estimating the cost
of compost plant are given in Table 9.
The construction waste and drain silt are washed in separate tanks, and then it can
be reused in various forms for construction work, e.g., making bricks and tiles, or
can be used as material for filling of low-lying areas.
Some amount of construction waste, if left unused, and the residue from the
compost plant is sent to sanitary landfill site which is designed for 10% of the total
waste in addition to the residue from compost plant. The relevant information for
cost estimation of sanitary landfill site is given in Table 10.
Thus the total cost of treatment was calculated by adding the cost incurred on all
three components of treatment, i.e., sorting station, compost plant, and sanitary
landfill. Annualized capex was computed by multiplying CRF with the total
capex. CRF values are taken to be 0.28 for equipment at an interest rate of 12%
with a loan period of 5 years and 0.134 for infrastructure at an interest rate of 12% for
a period of 20 years. Cost of electricity consumption was added in the opex. Annual
expenditure was determined and thus cost of total treatment per ton per day was
estimated.
Findings
Collection of Solid Waste
With door-to-door collection in our strategy to achieve the 100% collection, estima-
tion of cost of collection of municipal solid waste calls for calculating the required
amount of manpower and identifying vehicles to transport the waste collected from
households to larger vehicles which convey the waste to the transfer station.
The number of sweepers, pushcarts, pushcart workers, and storage bins required
were calculated after studying Detailed Project Reports (DPRs) of cities available
Table 9 Details/specifications of composting plant

S Fuel consumption
No Item Criterion/assumptions (liters per hour)
1 Loader cum 1 for 160 Mt of waste 12
excavator
2 Tipper (8 cum) 1 for 80 Mt of waste 8
3 Tractor tipper 1 for 160 Mt of waste 4
4 Water tanker 1 for 160 Mt of waste –
(3000 cum)
5 Computerized 1 for 30 Mt of waste –
weigh bridge
6 Plant machinery 1 Crore per ton –
7 Infrastructure 1 Crore per ton –
8 Manpower 22 skilled technicians + drivers, –
20 workers +25% extra
Table 10 Details/specifications of sanitary landfill site

S Fuel consumption (liters per
No Item Criterion/assumptions hour)
1 Loader 1 for 120 MT/day 12
backhoe
2 Tipper 1 for 60 MT/day 8
3 Bulldozer 1 for 120 MT/day 60
4 Landfill 1 for 120 MT/day 50
compactor
5 Manpower 4 skilled technicians, 15 workers –
+25% extra
and using the criteria described in Manual on Municipal Solid Waste Management –
CPHEEO – Ministry of Urban Development (2000). In an attempt to mechanize the
collection process, mini-waste collectors containing bins are proposed to collect
waste from residential and commercial areas.
The collection costs have been estimated by identifying the number of equipment
(pushcarts, mini-waste collectors) and manpower required and multiplying it with
rates of individual component. The estimated cost comes out to be INR 1224.53 per
ton per day. This includes the cost of equipment, manpower, fuel, and maintenance.
The costs were calculated by thoroughly studying available DPRs of cities like
Kanpur, Ghaziabad, and Vadodara as well as discussions with representatives of
several consulting firms.
The estimated fuel consumption in Class I towns is in the range of 0.03–0.05 l/t/
day with an average of 0.04 l/t/day and standard deviation of 0.01 which amounts to
an average cost of INR 2.05 per ton per day, and for Class II towns, the range is
0.001–0.04 l/t/day with an average of 0.02 l/t/day and standard deviation of 0.008,
amounting to an average cost of INR 1.22 per ton per day. There is no other energy
requirement in the collection process.
50 S. Gupta et al.
Fig. 3 Typical distribution of

estimated annualized capital
(capex) and operation and
maintenance (opex)
16%
expenditure on collection of
solid waste
OPEX
CAPEX
84%

3%
on collection of solid waste
16%
Push Carts
Storage bins
81% Mini Waste

Collectors
A typical pattern of distribution of estimated expenditure on waste collection

adopting the methodology described in section “Estimation of Capex and Opex of
Waste Collection” is presented in Figs. 3, 4, and 5.
It may be noted that in waste collection, the major expenditure is on operation and
maintenance (84%) which is on account of the high cost incurred on manpower
(82% of opex).
Conveyance of Solid Waste
Cost estimation for waste conveyance requires identification of equipment for

transfer station and vehicles for transporting waste to the sorting-cum-treatment
plant. The estimated cost for conveyance comes out to be INR 541.96 per ton per
day. This includes the cost of transfer station, equipment, vehicles, manpower, fuel,
and maintenance.

estimated operational
expenditure on collection of
solid waste
18%
Manpower
82%
Fig. 6 Typical distribution of

estimated annualized capital
(capex) and operation and
maintenance (opex)
expenditure on waste
conveyance
36%
OPEX
CAPEX
64%
The transportation of waste exerts a fuel requirement in the range of 0.28–0.61 l/t/
day with an average value of 0.43 l/t/day and standard deviation of 0.12, which
amounts to an average cost of INR 23.71 per ton per day for Class I towns. However,
for Class II towns, the fuel requirement is in the range of 0.11–0.49 l/t/day with an
average value of 0.26 l/t/day and standard deviation of 0.12, and subsequent average
cost is INR 14.11 per ton per day. The higher values correspond to towns with low
population density, and the lower values correspond to high population densities.
A typical pattern of distribution of estimated expenditure on waste conveyance
adopting the methodology described in section “Estimation of Capex and Opex for
Waste Conveyance” is presented in Figs. 6, 7, and 8.
It may be noted here that in waste conveyance, the opex (64%) is very high as
compared to capex (36%). This is due to the high amount of energy expenditure in
the form of fuel consumed in conveyance of the waste.
52 S. Gupta et al.

estimated capital expenditure 10% 2%
on waste conveyance
11%
Bins
Compactors
39% Dumper Placer Carriers
Hook Lifters
Infrastructure
38%

operation and maintenance
conveyance
Manpower
55% 45% Miscellaneous
(Inclusive of fuel)
Treatment of Solid Waste
The cost of treatment of solid waste is estimated with the consideration that maxi-
mum amount of waste is recycled and reused, landfill sites are minimized, and
efficient treatment options are adopted.
The municipal solid waste in India mainly contains organic or biodegradable
waste (60%); recyclable waste, i.e., plastics, metals, glass, and rubber (11%); and
drain silt and construction debris (29%). Prior to the treatment, segregation of the
total waste needs to be done so as to separate out recyclable waste from the rest and
then provide different types of treatment to different types of waste. Segregation
must be done at source which is not the case in India as people are not aware and
unwilling to manage the waste at household level. Therefore, a sorting-cum-treat-
ment plant is proposed. The whole treatment process can thus be divided into three
components as per the municipal solid waste distribution in India: (i) segregation,
(ii) composting, and (iii) landfill.
Estimation of the costs of these three components calls for preparing the flow
sheet and determining manpower requirement and equipment costs and energy
expenditure.
The total cost including capital investment (capex) and annual operation and
maintenance expenditure (opex) for such treatment has been worked out as INR
540 per ton per day. A typical breakup on expenditure made on solid waste
treatment and breakup of capex and opex on waste treatment are presented in
Figs. 9, 10, and 11.
It may be noted from the above figures that the infrastructure cost has a major
share (62%) in the total capital expenditure on waste treatment owing to the
construction of stations for sorting, composting, and landfill. Also, on account of
the mechanization of the sorting and treatment processes, less amount of manpower
is required, while fuel consumption is high.
The energy expenditure comes out to be INR 172.94 per ton per day of which
INR 160.16 is the cost of fuel per ton per day. A breakup of electricity and fuel on
energy expenditure is presented in Fig. 12.

capital (capex) and operation
and maintenance (opex)
treatment
OPEX
48%
52% CAPEX

on waste treatment
38%
Machinery
62% Infrastructure
54 S. Gupta et al.

estimated operational
treatment 16%
Manpower
Miscellaneous
84%

electricity and fuel on energy
expenditure in waste 7%
treatment
Electricity
Fuel
93%
Comprehensive Solid Waste Management System
The entire solid waste management system costs can be arrived at by adding the cost
of its three components, namely, waste collection, waste conveyance, and waste
treatment. The results are presented in Figs. 13 and 14.
It is important to note that waste collection has the major contribution in the total
annual expenditure. This is due to high opex in waste collection which results from
the heavy expenditure on manpower. Door-to-door collection and street sweeping
demand a good number of workers. Though waste sorting at source may improve the
collection efficiency and also increase the quantity of recyclable/reusable waste.
Analysis of the distribution of energy expenditure, which is mainly in the form of
fuel (diesel), depicts that waste treatment is the major contributor with 87% and 92%
share in Class I and Class II towns, respectively. The heavy equipment and machin-
ery such as loader backhoe, tractors, tippers, bulldozers, and compactors used in
composting and landfill consume high amount of fuel (Fig. 15).

estimated total annual
expenditure among three
components of solid waste 23%
management
Collection
Conveyance
58%
19%
Treatment
a b
16%
34% Collection Collection
40%
Conveyance 17% Conveyance
Treatment 67% Treatment
26%
Fig. 14 Typical breakup of estimated (a) capex and (b) opex among three components of solid
waste management
Estimated Costs of Provisioning Solid Waste Management

in Major Urban Agglomerations in Ganga River Basin
An attempt has been made to arrive at ballpark estimates for providing an appropri-
ate and complete infrastructure for solid waste management which is based on (i) the
methodology developed and results reported in the preceding sections of this chapter
and (ii) the information collated for urban agglomerations in Ganga River Basin
(GRB). Significant urban agglomerations are considered as Class I and Class II
towns defined on the basis of population (Class I towns, population 100,000; Class
II towns, population exceeding 50,000 and less than 100,000). A summary of
the total ballpark estimates of capital expenditures on provisioning solid waste
management for Class I and Class II towns of each of the GRB states is presented
in Table 11.
For each Class I and Class II towns of GRB, annual expenditure on the capital
investment (capex) for all three components of solid waste management systems has
been worked out by multiplying capital expenditure with capital recovery factor
(CRF). The CRF has been calculated as (i) 0.28 using 12% interest over 5-year
56 S. Gupta et al.
a 1% b 1%
7%
12%
Collection Collection
Conveyance Conveyance
Treatment Treatment
87% 92%
Fig. 15 Typical distribution of energy consumption in waste collection, conveyance, and treatment
of (a) class I and (b) class II towns
period for equipment and machinery and (ii) 0.134 using 12% interest over a 20-year
period for infrastructure and construction work. Operation and maintenance (opex)
has also been estimated for each of these towns for all three components. A summary
of the results for each of the GRB states is presented in Table 12 for Class I and Class
II towns.
Estimated per capita footprint, daily energy consumption, and daily expenditure
on availing appropriate solid waste management system for each of the Class I and
Class II towns in GRB are summarized in Tables 13 and 14.
It is interesting to note that footprint for waste treatment is approximately 0.7 m2
per person. The electrical energy consumption in complete solid waste management
comes out to be 0.001 KW-h per person per day, while the equivalent energy in the
form of fuel consumption is 0.017 KW-h per person per day for Class I towns, and
the corresponding value for Class II towns is 0.016 KW-h per person per day. The
fuel cost in waste collection and conveyance increases with decrease in population
densities. The total per capita expenditure for having complete solid waste manage-
ment system is estimated to be INR 1.15 per capita per day.
Discussion
Having proper solid waste management system in Indian Cities has many tangible
and intangible benefits. Some of the intangible benefits include improved aesthetics
of towns, lesser exposure to infectious diseases thereby substantial savings in
expenditure on health, lesser suffering and higher quality time available for mean-
ingful activities, etc. However, some of the tangible benefits include increased
amount of recyclable/reusable waste which in turn generates revenue, helps in
conserving resources, and reduces the amount of waste for treatment, thereby
decreasing treatment cost considerably. Compost from the composting plant can
be sold as manure to be used in agriculture, thus generating revenue and enhancing
crop yield. Further, construction debris and drain silt can be used for filling in
construction work, or they can be washed and made into bricks to be used for
2
Table 11 Estimated capital expenditure on solid waste management in Class I and Class II towns of NRGB
Estimated capital expenditure, millions of
INR
S Population in Estimated waste Waste Waste Waste Estimated total expenditure,
No State millions generation, MT/day collection conveyance treatment millions of INR
01 Uttarakhand 2.333 1167 174.25 346.79 637.42 1158.46
02 Uttar 32.722 16,361 2443.51 4862.88 8938.32 16244.71
Pradesh
03 Himachal
Pradesh No class I or II towns
04 Haryana 5.481 2741 409.26 814.47 1497.07 2720.80
05 Delhi 14.344 7172 1071.11 2131.64 3918.11 7120.86
06 Rajasthan 7.976 3987 595.59 1185.30 2178.65 3959.54
07 Madhya 12.588 6294 939.97 1870.67 3438.43 6249.07
Pradesh
08 Bihar 8.391 4195 626.56 1246.93 2291.95 4165.44
09 Chhattisgarh 3.586 1793 267.75 532.86 979.44 1780.05
10 Jharkhand 6.037 3019 450.80 897.15 1649.02 2996.97
Economic Assessment of Provisioning a Comprehensive Solid Waste. . .
11 West Bengal 18.124 9062 1353.38 2693.40 4950.66 8997.44

Total 111.582 55,791 8332.18 16582.09 30479.07 55393.34
57
58
Table 12 Estimated annual expenditure on solid waste management in Class I and Class II towns of NRGB
Estimated annual expenditure, millions of INR
S Population Estimated waste Waste collection Waste conveyance Waste treatment Total
No State in millions generation, MT/day Capex Opex Capex Opex Capex Opex Capex Opex
01 Uttarakhand 1223.2 1167 48.79 472.70 97.10 133.71 107.27 122.80 253.16 729.21
02 Uttar 19206.5 16,361 684.18 6628.47 1361.60 1874.91 1504.22 1721.98 3550.00 10225.36
Pradesh
03 Himachal
Pradesh No class I or II towns
04 Haryana 5.481 2741 114.59 1110.19 228.05 314.02 251.94 288.41 594.58 1712.62
05 Delhi 14.344 7172 299.91 2905.58 276.61 821.87 659.38 754.83 1235.90 4482.28
06 Rajasthan 7.976 3987 166.77 1615.65 331.89 457.00 366.65 419.73 865.31 2492.38
07 Madhya 12.588 6294 263.19 2549.86 523.79 721.25 578.65 662.41 1365.63 3933.52
Pradesh
08 Bihar 8.391 4195 175.44 1699.66 349.14 480.77 385.72 441.54 910.30 2621.97
09 Chhattisgarh 3.586 1793 74.97 726.33 149.20 205.44 164.83 188.69 389.00 1120.46
10 Jharkhand 6.037 3019 126.23 1222.88 251.20 345.90 277.51 317.69 654.94 1886.47
11 West Bengal 18.124 9062 378.95 3671.30 754.15 1038.45 833.14 953.75 1966.24 5663.50
Total 111.582 55,791 2333.02 22602.62 4322.73 6393.32 5129.31 5871.83 11785.06 34867.77
S. Gupta et al.
2
Table 13 Estimated footprint, energy consumption, and expenditure on solid waste management in class I towns of NRGB
Estimated annual
Estimated land Estimated daily Equivalent energy Energy Expenditure on solid waste
S Population required per capita fuel demand in (fuel) consumption in consumption management in millions of
No State in millions in m2 liters MWH in MWH INR
01 Uttarakhand 2.121 5.6 3509.2 12808.6 828.8 892.95
02 Uttar 29.613 43.4 54503.8 198939.0 11570.9 12466.61
Pradesh
03 Himachal
Pradesh No class I town
04 Haryana 5.317 11.2 9496.2 34661.0 2077.5 2238.33
05 Delhi 13.482 10.5 29001.0 105853.5 5267.9 5355.38
06 Rajasthan 7.689 13.3 15806.1 57692.1 3004.3 3236.91
07 Madhya 11.934 18.9 22173.8 80934.5 4662.9 5023.86
Pradesh
08 Bihar 6.929 19.6 11750.2 42888.1 2707.3 2916.82
09 Chhattisgarh 3.138 6.3 5779.1 21093.9 1226.1 1320.99
10 Jharkhand 4.801 10.5 8456.3 30865.4 1876.0 2021.21
Economic Assessment of Provisioning a Comprehensive Solid Waste. . .
11 West Bengal 17.124 43.4 29710.4 108443.0 6690.8 7208.74

Total 102.148 182.7 190186.1 694179.1 39912.5 42681.80
59
60
Table 14 Estimated footprint, energy consumption, and expenditure on solid waste management in class II towns of NRGB
Estimated annual
Estimated land Estimated daily Equivalent energy Energy Expenditure on solid waste
S Population required per capita fuel demand in (fuel) consumption in consumption management in millions of
No State in millions in m2 liters MWH in MWH INR
01 Uttarakhand 0.212 2.8 332.1 1212.3 83.0 89.42
02 Uttar 3.109 30.1 4888.5 17843.0 1214.7 1308.75
Pradesh
03 Himachal
Pradesh No class II town
04 Haryana 0.164 2.1 255.1 931.2 63.9 68.87
05 Delhi 0.862 9.8 1307.8 4773.4 336.7 362.80
06 Rajasthan 0.287 2.8 471.9 1722.3 112.1 120.76
07 Madhya 0.654 7.0 1040.4 3797.6 255.5 275.31
Pradesh
08 Bihar 1.462 16.1 2316.5 8455.2 571.2 615.45
09 Chhattisgarh 0.448 4.2 779.6 2845.4 174.9 188.48
10 Jharkhand 1.236 11.9 1994.8 7281.2 482.8 520.20
11 West Bengal 1.000 10.5 1601.7 5846.4 390.8 421.01
Total 9.433 97.3 14988.4 54,708 3685.6 3971.05
S. Gupta et al.
construction purposes again. Slowly progressing toward the goal of “minimum

landfill” concept ensures good quality of agricultural land availability and no
groundwater or surface water hazards.
The following conclusions may be drawn based on the synthesis of the informa-
tion available in the literature and the results obtained from this study.
• Typical breakup of total annual expenditure on solid waste collection between

capex and opex is 16% and 84%, respectively.
• Manpower alone contributes to about 82% of the total opex incurred in solid
waste collection.
• Typical breakup of total annual expenditure on solid waste conveyance between
capex and opex is 36% and 64%, respectively.
• Approximately 10% of total capital expenditure on solid waste conveyance is the
cost incurred on transfer station.
• The total share of miscellaneous cost inclusive of fuel and maintenance cost
comes out to be 55% in case of waste conveyance which is very high as compared
to 18% as was in the case of waste collection.
• Typical breakup of total annual expenditure on waste treatment between capex
and opex is 48% and 52%, respectively.
• Infrastructure cost contributes to 62% of the total capital expenditure in waste
treatment, while the cost of machinery is 38% of the total capex.
• Approximately 84% of the total opex is incurred on manpower, while the
miscellaneous cost has a share of 16% in the total opex.
• Approximately 58, 19, and 23% of the total annual expenditure on solid waste
management are incurred on waste collection, conveyance, and treatment, respec-
tively, in a typical Indian town.
• About 34%, 26%, and 40% of the total capital expenditure on solid waste
management are toward waste collection, conveyance, and treatment, respec-
tively, while about 67%, 17%, and 16% of the total operational expenditure are
incurred in waste collection, conveyance, and treatment, respectively.
• Approximately 87% of the energy bill is toward waste treatment, 12% is due to
waste conveyance, while only 1% of energy expenditure is incurred on waste
collection for Class I towns.
• For Class II towns, 92% of the energy bill is toward waste treatment, and 7% is
due to waste conveyance, while only 1% of energy expenditure is incurred on
waste collection.
• Total annual capex and opex for provisioning solid waste management in all Class
I and Class II towns of GRB is expected to be INR 11785.06 and 34867.77
million, respectively. This amounts to average per capita per day expenditure of
INR 1.15.
• The average per capita per day energy consumption in availing solid waste
management comes out to be 20 W hour for Class I towns and 17 W hour for
Class II towns.
• The expenditure on solid waste may be justified in GRB based on tangible and
intangible benefits.
62 S. Gupta et al.
Conclusion
Status of municipal solid waste management in India is very poor, where most of
the environmental challenges and their remediation often receive a neglected
budget allocation. Allocation of financial resources for infrastructure development
is a critical challenge for a developing country like India. In general, solid waste can
be seen littering around, and even colonies can be seen being developed on the pile
of this waste. The ideal disposal and treatment methods have not been implemented
in most of the towns, and hence a comprehensive solid waste management plan is
needed to be prepared. The present chapter attends to this need and a comprehensive
framework to arrive at ballpark estimates of providing a complete SWM plan with a
goal to promote reuse/recycling of waste and achieve minimal landfill. Studies have
shown that inadequate manpower, financial resources, and implements/machinery
required to effectively carry out various activities of MSWM are not comprehen-
sively invested upon in India (Kumar et al. 2009).
However, the per capita expenditure on providing comprehensive SWM infra-
structure shows that expenditure is very affordable; furthermore, for successful
implementation of such a framework, resource recovery is an important aspect and
is addressed within the chapter. Individuals and firms willing to adapt any of the
methodologies outlined here are welcome to do so and are most cordially invited to
contact the author to explore options for sharing data, materials, and expertise.
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Decentralized Integrated Approach of
Water and Wastewater Management in 3
Rural West Bengal
Pankaj Kumar Roy, Somnath Pal, Arunabha Majumder,

Gourab Banerjee, and Asis Mazumdar
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
Overview and Scope of Surface Water Supply and Integrated Supply . . . . . . . . . . . . . . . . . . . . . . 67
Conceptualization and Design Parameters of Water Supply Scheme . . . . . . . . . . . . . . . . . . . . . . . . 68
Study Area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
Geography Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Rainfall . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
Catchment Area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
Catchment Area and Reservoir Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Silt Trap Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Surface Water Treatment System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
Horizontal Roughing Filter (HRF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Slow Sand Filter (SSF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Activated Carbon Filter (ACF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Wastewater Treatment System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
Horizontal Reed Bed Filter (Ref. Fig. 6) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
Design Criteria of Reed Bed (Horizontal) Filter System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
Design Specification Reed Bed (Horizontal) Filter System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
Design Parameter of Reed Bed (Horizontal) Filter System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Results of Physicochemical Parameter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Percentage (%) of Removal Efficiency of Physicochemical Parameter of Final Treated
Effluent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Result and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
P. K. Roy (*) · S. Pal · G. Banerjee · A. Mazumdar

School of Water Resources Engineering, Jadavpur University, Kolkata, West Bengal, India
A. Majumder

https://doi.org/10.1007/978-3-319-73645-7_2
66 P. K. Roy et al.
Abstract
The issue of water availability and wastewater management is a common scenario
all over the world. Delay in summer and soaring temperatures have massively
reduced the existing stock of water resources in the past few decades. Drying up
of small surface water sources like pond, lakes, etc., decline in groundwater table,
deterioration of water quality, and poor wastewater management are some of the
current problems encountered in both urban and rural areas in India. West Bengal,
particularly Murshidabad, Nadia, North 24 Parganas districts, etc., are highly
affected by arsenic rather than other mineral’s presence. Apposite management
strategies and safety planning play a crucial part to combat these problems to
some extent. This study highlights the role of catchment area management
ensuring safety of potential source of drinking water and also quantifies waste-
water generated from households, and finally a sustainable eco-friendly techno-
logical solution is to be developed at project site. The sources of water flowing
into the pond are mainly rainfall, rainfall-mediated agricultural runoff generated
during monsoon season as a result of heavy rainfall, and some domestic waste-
water generated from individual households. The gray water is treated using reed
bed filter through a horizontal flow system. A silt trap designed with the help of
input parameters is placed at the suitable location to arrest sediment loads
particularly in rainy season while transporting surface runoff in the defined
catchment. Water and wastewater quality has been analyzed by using different
instruments prescribed by APHA guideline. The raw water is treated by aeration,
horizontal roughing filter, slow sand filter, activated carbon filter, and post
chlorination with optimum dosages. In addition also wastewater could be treated
using an eco-friendly technique like reed bed filter. This type of integrated water
and wastewater treatment system if established may provide an alternative source
of drinking water where sufficient pond systems exist under deteriorated ground-
water quality condition, and also treated wastewater may be used for irrigation
and other purposes with zero discharge at the end of the day.
Keywords
Horizontal roughing filter · Slow sand filter · Activated carbon filter · Silt trap ·
Reed bed filter
Introduction
Arsenic contamination of groundwater has led to endemic condition of arsenic

poisoning in Eastern India, Bangladesh, and neighboring countries. Chronic arsenic
pollution is now recognized as a worldwide problem, with 21 countries experiencing
arsenic groundwater contamination. Today, arsenic contamination in groundwater is
found to be affecting 79 blocks of 8 districts of West Bengal, namely, Maldah,
Murshidabad, Nadia, North 24 Parganas, South 24 Parganas, Burdwan, Hooghly,
and Howrah and also in 11 municipal areas and 18 non-municipal outgrowth areas
3 Decentralized Integrated Approach of Water and Wastewater Management. . . 67
(AIIH and PH 2007). It is a particularly important issue in rural areas of developing

countries, where untreated groundwater is generally the preferred drinking source as
piped water supply schemes are not in place (Roy et al. 2015). The issue of water
availability and wastewater management is a common scenario all over the world.
Delay in summer and soaring temperatures have massively reduced the existing stock
of water resources in the past few decades. Drying up of small surface water sources
like pond, lakes, etc., decline in groundwater table, deterioration of water quality, and
poor wastewater management are some of the current problems encountered in both
urban and rural areas in India. For this purpose, Department of Science and Technol-
ogy (DST) sponsored and Indian-European Consortium collaborated project namely
“Energy-efficient community-based water and wastewater treatment systems for
deployment in India” (ECO-India), which was implemented to the challenge by
delivering substantial innovation using conventional and leading Indian-European
novel technologies combined with advanced research. In order to deploy reliable
and cost-effective solutions, arsenic removal treatment system from arsenic prone
groundwater source and ecological surface water treatment system as an alternative
source of arsenic-free drinking water treatment technology were developed for rural
areas at JyotSujan village, Murshidabad District, West Bengal, India (Roy et al. 2016).
Overview and Scope of Surface Water Supply and Integrated Supply
Surface water usage for human consumption implies taking a special care of typical
surface water contaminants related to serious diseases, e.g., diarrhea, hepatitis,
typhoid fever, and cholera. Thus, awareness on quality maintenance and sound
technologies for the treatment are prerequisites for a successful usage.
Surface water supply scheme setup is that all stages of the local and regional
water cycle are being tackled. The quality of the water resources is to be improved.
Integrated Water Resource Management will have to involve all the user groups in
the watershed including farmers and fishers among other economic and domestic
water users. Pollution sources have to be identified and water resource protection
measures put into place.
The treatment process is conceptualized so that no external electrical power and
as less as possible chemical consumables are needed. In order to achieve this, the
pumping power is sourced by photovoltaic cells, and the raw water and clear water
tanks are dimensioned to cater sufficient water to the filter units in order to make
them run continuously for 24 h a day.
The piped water is protected from external contamination, and better quality
control through monitoring is possible. The 24/7 supply ensures suitable quality at
the point of collection by not letting any contamination infiltrate into the distribution
network due to continuous positive pressure in the pipeline.
Having laid a distribution network to the consumer and assuming individual
sanitation installations with flushed toilets, the wastewater collection has to be set
up at the same time. The construction at the same point of time is efficient from the
point of view of having to do earthen works only once.
68 P. K. Roy et al.
Conceptualization and Design Parameters of Water Supply Scheme
The needs assessment and participatory planning process led to the conceptualiza-
tion of surface water-based drinking water supply system which is augmented with a
groundwater scheme. The source of the surface water supply is a village pond of
7300 m3 capacity with adjacent 25,000 m2 catchment area which is engineered with
bunds and harvesting cannels. Farmers in the region are keen in introducing organic
farming in order to protect the water source. Contrary to many studies reporting
hesitations by local populations in using pond water as drinking water source, the
local population is convinced that the surface water is a safe alternative to the
contaminated groundwater. The basic treatment process for the drinking water
consists of horizontal roughing filters and slow sand filters (HRF/SSF) and activated
charcoal filter with modifications to established concepts (Wegelin 1996) with recent
research results (Pereira 2012). The gravity-based filtration process and distribution
is run by solar power, making it a green technology setup mitigating climate change.
The wastewater is treated with a wastewater settling tank (WWST) and a waste-
water reed bed system (WWRBS). Community members are eager to connect their
houses to the water supply network and upgrade their sanitation unit to flushed
toilets connected to a sewer line. In the second step, the basic filtration process is
upgraded with state-of-the-art activated carbon filter media filtration and enhanced
disinfection by mixed oxidants or liquid chlorine. The overall process is monitored
online with sensors as well as verified by offline laboratory measurements (SWRE,
JU, Eco-India (D 1.6) 2012).
Study Area
The village JyotSujan was located at Dahapara GP, Murshidabad-Jiaganj Block,

Murshidabad District, WB, having latitude 24 90 11.2300 and longitude 88 150 24.0600 .
The JyotSujan settlement has a population of approx. 2000 out of which approx.
1500 are above 18 years belonging to about 250 households. There are 200 pupils
studying in primary school and 50 children in ICDS (integrated child development
service); JyotSujan has a community mosque where about 100 people offer prayers.
The Malpara settlement has a population of approx. 400. The main occupation of both
communities is farming, 40% of the surveyed people are farmers, and women are mostly
housewife which amounts to 45% of the surveyed population. Apart from farmers, there
are some people doing labor jobs on a daily basis, and survey shows about 14% are
labors. Fishery and animal husbandry are also a source of income for the villagers. The
average monthly income for each household ranges from 1500 to 4500 INR.
The entire village was categorized as North (N), West (W), South (S), South East
(SE), and South West (SW) for site selection of integrated scheme. Based on the
preliminary results from evaluation of socioeconomic survey, 98% of the respondents
are interested in being covered by the integrated scheme, and several reasons indicate
the selection for location of the integrated scheme in favor of the Malpara part of the
village for maximum monetary contribution toward infrastructure maintained and
evident water transport and sanitation problems. The next possible location for the
integrated scheme could be the SE and or SW part of the village for higher open
defecation practices and water transport problems. In regard to the catchment area
protection from contamination through open defecation, Malpara and the south part of
JyotSujan also provide the highest risk potential as the local population chooses
locations in the catchment area of the pond for their defecation (Pal et al. 2015).
The general needs identified by the interview partners are provision of safe
drinking water, improvement of sanitation facilities, and increase of awareness on
hygienic practices regarding water contamination. Further solid waste and wastewa-
ter management would be welcome. Finally, all important locations were agreed
upon in the water committee.
The surface treatment system water scheme covers the Malpara settlement with
stand posts and parts of south JyotSujan settlement with house connections. The
surface water treatment plants consist of the horizontal roughing filter, slow sand
filter and activated carbon filter, which is located on the adjacent north-facing plot of
the pond (SWRE, JU, Eco-India (D 1.6) 2012).
Geography Assessment
JyotSujan and Malpara are partly in the Diar Chaitanpur and partly in the Khosbag
Mouza of Murshidabad-Jiaganj Gram Panchayat in the Murshidabad District. The
next bigger village Khosbag is 2 km away, Murshidabad is 5 km away reachable by
ferry, and Berhampore is around 15 km away reachable by road. Kolkata is around
220 km away and can be reached by train in around 4–4.5 h or by road in 6–7 h. The
village is situated in the plains of the river Bhagirathi, flowing 300–700 m away from
the settlement with a flow rate of approx. 40,000 m3/s. The village surroundings are
grasslands used for animal husbandry, ponds for aquaculture, and agricultural field
used for growing rice, wheat, pulses, spices, and vegetables. Fruits are mainly grown
in mango orchard and banana garden. There are substantial use of chemical fertilizer,
pesticides, and insecticides in the agricultural field (paddy, vegetable, fruits (Mango
orchards)) and usage of medicines and food for the aquaculture in the ponds. The soil
is hard clayey alluvial soil. The fields are irrigated with flood irrigation fed by the
water from the river Bhagirathi and shallow or deep tube wells partly canalized to the
fields. The agricultural runoff goes to the river Bhagirathi. The topsoil is sandy alluvial
(mix of sand and clay), and in different strata, sand and clay layers are present with
partly clay patches. For a soil mixture of sand, silt, and clay, the assumed hydraulic
conductivity is found to be 0.1 m/day. The temperature in the area is ranged between
min 8 and max 43 C in a year. The below graph shows the fluctuation of monthly
minimum and maximum temperature over a period of 5 years. The rainy season
stretches from June to September, and the average annual rainfall is 1400 mm. The
annual average wind speed is found to be 2.64 m/s with the monthly distribution
shown below which is relevant for the running windmills. All data has been collected
from different govt. and private organizations. The basic wind speed is nearly 50 m/s
used for design criteria of structures (SWRE, JU, Eco-India (D 1.6) 2012).
70 P. K. Roy et al.
Table 1 Water quantity assessment for identified potential water bodies

All measurements in meter
Pond Rainy season (maximum) Dry season (minimum) Excavated potential Water
s. ID L W D Capacity L W D Capacity L W D Capacity quantity
1 17 21.5 6 2193 21.5 17 2 731 24 19.5 5 2340 11
2 21 19 3.5 1396.5 19 17 1 323 21 19 5 1995 13
4 34 28 3.5 3332 31 25 0.5 387.5 36 28 5 5040 6
5 35 21 3.5 2572.5 32 18 0.5 288 35 21 5 3675 8
6 75 43 4.5 14512.5 73 41 2 5986 75 43 5 16,125 2
7 60 52 3 9360 56 49 0.5 1372 60 52 5 15,600 3
8 26 13 2.5 845 25 12 0.5 150 27.5 13 5 1787.5 14
9 30 55 4 6600 28 53 2 2968 33 58 5 9570 4
10 59 56 5 16,520 57 54 2.5 7695 59 56 5 16,520 1
11 12 18 3 648 16 9 1 144 12 18 5 1080 16
12 41 12 2.5 1230 39 11 0.5 214.5 41 12 5 2460 10
13 26 10 4.5 1170 25.5 9.5 1.5 363.375 26 10 5 1300 15
14 13.5 30.5 3 1235.25 30 13 0.5 195 13.5 30.5 5 2058.75 12
15 38 27 3 3078 35 25 0.5 437.5 38 27 5 5130 7
16 52 35 4.5 8190 50 30 0.5 750 54 35 5 9450 5
Rainfall
The rainfall data for the catchment is collected from site of India Meteorological
Department, Govt. of India. The average annual rainfall is found to be 1400 mm,
where the rainy season stretches from June to September. A 5-year monthly distri-
bution of rainfall data (shown in Fig. 3) is analyzed to understand any changes in
rainfall pattern over the 5-year period. For example, surface water (pond) source
based integrated water supply scheme implemented where the rainfall and rainfall-
associated surface runoff is the main source of groundwater recharge. The analysis of
the past 5-year rainfall pattern provides a reasonable estimate (SWRE, JU, Eco-India
(D 1.6) 2012).
The average annual solar intensity is found to be 4.58 Kwh/m2/day in the pilot
site collected from secondary sources (Table 1).
From the water quantity point of view, it is evident that the pond 10 is best
suitable followed by pond 6, pond 7, and pond 9.
Catchment Area
An assessment of the available and required catchment area is made. The identified
catchment area should provide enough runoff during the rainy seasons to recharge
the pond and meet the expected water demand of the community served by the
integrated scheme. The results of the assessment are shown in Fig. 1.
Catchment Area and Reservoir Management
The catchment area is required to provide enough water into the pond to supply
~20 KLD, throughout the year. The surface water source is expected to meet a water
demand between 14 and 28 KLD (20 KLD in average is considered for the further
calculation). It is estimated by creating a water balance model with available
hydrological and climatic data, like precipitation, evaporation, infiltration, etc. as
shown in Table 3. According to the water balance model, net storage water of pond is
also given in Table 2.
For the calculation, the first approach is to estimate the precipitation retention in
the pond due to rain falling on its surface. The evaporation values of each month are
deducted from corresponding monthly precipitation values to identify a net
Fig. 1 Elevation measurement in the potential catchment area of 35,000 m2 and potential bunds
and channels
Table 2 Parameters for Parameter Unit Value

calculating the net storage
Length of pond m 60
of the pond
Breadth of pond m 32
Wetted pond area m2 920
Catchment area m3 20,300
Daily demand KLD Up to 28
72
Table 3 Catchment area inflow and pond water availability in around 14,000 m2 catchment area
Infiltr Net storage from Demand Runoff Flood water Storage real First
Prep. Evapo (1 mm/ prep. over pond (cu.m/ received after contribution (cu.m) Storage (max. size flush
Months (mm) (mm) day) (cu.m) day) losses (mm) (14,000 m2 catchment) change 7330 m3) m3
Jan 2 62 31 143 0 0 0 143 6126
Feb 13 84 28 162 0 0 0 162 5964
Mar 21 155 31 287 0 0 0 287 5677
Apr 33 210 30 368 0 0 0 368 5309
May 104 217 31 246 0 0 0 246 5063
Jun 287 180 30 178 0 103 1410 589 589 1000
Jul 278 155 31 208 0 111 1529 1737 2326
Aug 281 124 31 273 0 132 1815 2089 4414
Sep 284 90 30 344 0 135 1858 2202 6616
Oct 95 93 31 25 0 0 0 25 6592
Nov 1 90 30 199 0 0 0 199 6392
Dec 13 62 31 123 0 0 0 123 6269
Total 1410 1522 365 551 0 481 6613 5063
P. K. Roy et al.
precipitation in mm. Multiplying the net precipitation values with surface area of the
pond gives the net precipitation in m3. Infiltration rate at pond sides and bottom is
assumed to be 1 mm/day (considering silty clay). Multiplying the infiltration rate to
wetted surface area of the pond gives the infiltration losses in m3/day. A cumulative
monthly infiltration loss is deducted from the monthly net precipitation values to get
the net storage values due to precipitation over pond.
The second approach is to estimate the required runoff to meet the water demand
of 20 KLD and corresponding catchment area required to generate the runoff.
It is assumed that for months with higher precipitation values than evaporation
values, an amount of runoff equal to the difference generates. Deducting assumed
storage losses at 10% and infiltration loss as 1 mm/day from the generated runoff, the
depth of runoff received at the pond is estimated. The received runoff in mm is
multiplied with the variable catchment area to give the runoff volume received at
the pond.
To identify the monthly storage changes in the pond, the demand values are
deducted from the sum of net storage from precipitation over pond and flood water
contribution values.
The monthly storage potential is identified by cumulating the storage change
values, starting from the first positive storage change value. Later the catchment area
variable is iterated to find an optimum catchment size where all the monthly storage
potential values are positive. Thus, a required catchment area of 20,300 m2 is
identified, which is equivalent to a runoff rate k = 0.2 (considered). This would
result in a catchment area of 34,600 m2. The total assessed potential catchment area
is the vicinity of the pond which is 35,000 m2; thus, the entire potential would need
to be drained to the pond.
The catchment area assessed surrounding the selected pond no. 9 and is shown in
Table 3. The thick blue lines show the channels required to transport the runoff to the
pond. The adjacent thin green lines signifies the catchment area protection bunds
required to minimize the runoff contamination from adjacent fields and to directs the
runoff through the channels (SWRE, JU, Eco-India (D 1.6) 2012).
Silt Trap Design
A 3 10 m silt trap with 1.5 m height will be set up to control the inflow of
sediments into the pond; the silt trap also has a shutter to prevent the first flush run
off from the fields to enter the pond. The dimensions of the silt trap are given in
Figs. 2 and 3.
From Table 4, the silt trap load calculation is observed that the total suspended
solid (TSS) of runoff water (rainy season) which comes out from catchment area and
collected into silt trap is 1 mg/L (avg.). According to the sediment load, the estimated
sludge volume 2.94 m3 (wet basis) per year is generated in silt trap. So total time
required to fulfill the silt trap is 16 years. But deposited sediment load should be
removed every year to achieve better performance purpose (SWRE, JU, Eco-India
(D 1.6) 2012).
74 P. K. Roy et al.
Fig. 2 Top view plan of silt trap
Fig. 3 Sections of silt trap
Table 4 Silt Parameter Unit Value

trap-sediment load
Total volume of silt trap m3 23.175
specification
Total volume required silt load Kg 64030.5
Generation of total sludge volume/year m3 2.94 (wet basis)
Total time required for full storage Yr 16
Surface Water Treatment System
The composite treatment process consists of horizontal roughing filter, slow sand
filter, and activated carbon filter. For this system, the only photovoltaic solar pump
(1 hp) is used to withdraw pond water (Raw) for surface water treatment process.
The HRF was fed from the raw water (surface (pond) water storage) tank and from
the HRF, the water flowed into the SSF and it passes through the ACF and then
stored into the treated water reservoir.
The source of the surface water supply is a village pond of 7300 m3 capacity with
adjacent 25,000 m2 catchment area which is engineered with bunds and harvesting
cannels. Farmers in the region are keen in introducing organic farming in order to protect
the water source. The basic treatment process for the drinking water consists of horizontal
roughing filters, slow sand filters (HRF/SSF), and activated charcoal filter with modifi-
cations to established concepts (Wegelin 1996) with recent research results (Pereira
2012). The gravity-based filtration process and distribution is run by solar power, making
it a green technology setup mitigating climate change. In the second step, the basic
filtration process is upgraded with state-of-the-art activated filter media filtration and
enhanced disinfection by mixed oxidants. The overall treatment process is then moni-
tored online with sensors as well as verified by offline laboratory measurements.
Horizontal Roughing Filter (HRF)
Basically, two horizontal roughing filters are placed parallel. The length, breadth,
and height of each HRF are 5.8 m, 0.73 m, and 1 m, respectively. HRF basically
removes turbidity (<10 NTU). The specifications for the horizontal roughing filter is
based on a flow rate of 0.5 m/h in case of both filter units running and 1 m/h in case
of only one unit running.
Slow Sand Filter (SSF)
There are two parallel slow sand filters. The length, breadth, and height of each SSF are
4 m, 0.73 m, and 2 m, respectively. The grain size has been chosen as 0.2 mm for a 99%
removal of total coliform. Test runs with smaller grain size up to 0.1 mm are foreseen to
increase the removal efficiency. The basis for the design is a flow rate of 0.1 m/h in case
of two filter units running parallel and 0.2 in case of only one unit running. The grain
size has been chosen as 0.2 mm for a 99% removal of total coliform. Test runs with
smaller grain size up to 0.1 mm are foreseen to increase the removal efficiency. The basis
for the design is a flow rate of 0.1 m3/h in case of two filter units running parallel and
0.2 m3/h in case of only one unit running as depicted in Figs. 4 and 5.
Activated Carbon Filter (ACF)
There are two parallel horizontal roughing filters. The length, breadth, and height of
each ACF are 0.85 m, 0.73 m, and 2 m, respectively. ACF is used to remove color and
order purposes of treated drinking water. The design specifications of the activated
carbon filter are based on a contact time of max. and minimum 50 min and 25 min,
respectively, in case only single filter is running (Roy et al. 2016). A complete surface
water treatment operational system specification is shown in Table 5.
76 P. K. Roy et al.
Raw water tank
Roughing filter: 5, 10, 15mm chambers
1.00
1.00 1.50 2.00

5.80
0.40
max water level0.75
min water level 0.10 0.85 2.00

max sand level
0.90 0.50
0.40
min sand level 0.25
4.00 0.85
slow sand filter with gravel bed optional activated
at the bottom for collection of carbon filter for
Clear
filtered water final polishing
water tank
5.80
Fig. 4 HRF, SSF, ACF design (section and plan view)
In composite surface water treatment, turbidity and bacteria removal efficiency is

90–93.33 and 57.14–50.44% in HRF-1, 93.33–94.66 and 54.33–57.71% in HRF-2,
99.0–99.33 and 97.33–99.92% in SSF-1, and 98.8–99.0 and 99.14–99.92 in SSF-2,
respectively, shown in Tables 6 and 7. And DO level in normal in all components.
So, it showed that removal efficiency of HRF-2 is better than HRF-1. It means that
better removal is achieved in different size of gravel media than stone chips media
due to its effective porosity (media shape and size). And all SSF (1 and 2) perfor-
mance is better according to their removal efficiency. After passing, ACF (1 and 2)
color and odor removal is successfully possible. Finally, it stored to clear water
storage tank and disinfects with liquid chlorine or mixed oxidant (proper dose) and
supply the treated water ready with distribution pipe lines to different stand post.
Wastewater Treatment System
Horizontal Reed Bed Filter (Ref. Fig. 6)
The schematic cross section of a horizontal flow-constructed reed bed filter is

showed in Fig. 6. As the name states, the wastewater is fed in the inlet and flows
slowly through the porous substrate under the surface of the bed in a more or less
Fig. 5 Composite surface

water treatment scheme
horizontal path until it reaches the outlet zone. During this passage, the wastewater
will come into contact with a network of aerobic, anoxic, and anaerobic zones. The
aerobic zones will be around the roots and rhizomes of the wetland vegetation that
leak oxygen into the substrate. During the passage of wastewater through the
rhizosphere, the wastewater is cleaned by microbiological degradation and by
physical and chemical processes. This type of filter can effectively remove the
organic pollutants (TSS, BOD5, COD) from the wastewater. Due to limited oxygen
transfer inside the wetland, the removal of nutrients is limited (SWRE, JU, Eco-India
(D 1.6) 2012).
The design (length-width ratio, depth, hydraulic loading rate, hydraulic residence
time, plant species, soil mixture, and so on) depends on site-specific facts (type of
wastewater, topography) and on degradation kinetics typical for reed bed treatment
systems – in most cases a first-order reaction. The necessary area or volume is further
calculated to meet the officially required discharge limits. Besides proper construc-
tion and planting of these artificial wetlands, specialists should supervise the initial
phase of the ecosystem development to avoid malfunctions of the total pollution
control concept.
78 P. K. Roy et al.
Table 5 Detail surface water treatment system specifications

Parameter Variable Unit Value
Possible supply surface water scheme Dsws KLD 12.73
Process water 10% Dprocess 1.27
Total water to be produced Dtotal KLD 14.00
Flow if continuous filtration of raw water Qcft LPH 583.24
Time no pump 18 h (20 h for security) tnp Hours 20.00
Capacity raw water reservoir size Crw KL/m3 11.66
No of filter units Npump No 2.00
Flow continuous filtration of 1 unit Qft LPH 291.62
HRF specification
Filtration rate vF m3/h 0.50
Area cross-sectional filter Acsf m2 0.58
Initial total head loss HL m 0.06
SSF specifications
Filtration rate vF m3/h 0.10
Area filter bed Afb m2 2.92
Diameter grain size filtration media dfm mm 0.20
Uniformity coefficient (d60/d10) UC 3.00
Initial head loss HLfm m 0.16
ACF specification
Contact time Tc h 0.8
Area filter bed Afb m2 0.58
Diameter grain size filtration media Dfm mm 5
Initial head loss HLfm m 0.0056
Table 6 Result of water quality parameter of entire surface water treatment scheme
Source Turbidity (NTU) pH DO (mg/L) Bacteria (MPN per 100 ml)
Pond water 30–150 7.8–8.2 3.07–5.04 350–10,000
HRF-1 3–10 7.8–8 3.16–3.7 150–4956
HRF-2 2–8 7.75–7.9 3.1–3.79 148–4567
SSF-1 0.2–1.5 7.59–7.8 2.6–5.6 4–8
SSF-2 0.3–1.8 7.51–7.72 3.1–5.3 3–8
Table 7 Percentage (%) Source Turbidity (NTU) Bacteria (MPN per 100 ml)
Removal of water quality
HRF-1 90–93.33 57.14–50.44
parameter
HRF-2 93.33–94.66 54.33–57.71
SSF-1 99.0–99. 33 97.33–99.92
SSF-2 98.8–99.0 99.14–99.92
1.08 m
15 mm gravel 10 mm gravel 5 mm gravel
1.08 m
Well Colletion pit Holding Tank
1.4 m
1.4 m
0.25 m 0.6 m
1.4 m 3m 0.6 m 0.25 m
Perforated wall
Colletion pit PLAN
GL
Plants
100 mm
100 mm
Holding Tank
100 mm
0.6 m
Inlet
0.4 m
15 mm gravel 10 mm gravel Out let
5 mm gravel
1.08 m
0.6 m
1
50
0.25 m 0.6 m 3m 0.6 m 0.25 m
Perforated wall
SECTION
Fig. 6 Reed bed filter
Reed bed treatment systems have been successfully used for treating a wide range
of wastewater concentrations, from the very dilute up to COD concentrations of
20,000 mg/l and nitrogen concentrations of 4000 mg/l. They can also handle a wide
range of effluent throughputs ranging from small and intermittent flows of about
1 m3/day to several 10,000 m3/day.
Factors influencing the purification process of reed bed treatment systems:
1. Hydraulic loading rate (m3/[ha d]) and hydraulic detention time (d)
2. Temperature
3. Influent pollutant concentration
4. Oxygen supply
5. Development stage of the reed ecosystem (This sequence is in random order, not
according to quantitative importance)
Settlement or Holding Tank (Ref. Fig. 7)

A settlement or sedimentation tank is arranged to settle organic substances. Its
operation capacity depends on the retention time of the sewage, surface loading
and flow velocity. The tanks are designed so that even at maximum inflow good
sedimentation efficiency is achieved. The retention time in this case is about
1.5 days. The possibility for sewage sludge utilization depends on site-specific
80 P. K. Roy et al.
Fig. 7 Typical section of

settlement tank
Table 8 Design Parameter Unit Value

specification of
Supply of drinking water LPCD 40
holding tank
Total population Persons 30
Gray water generation LPCD 22
Total gray water generation L/day 660
Considered L/day or m3/day 700 or 0.7
Depth of holding tank m 0.6
Area m2 1.166667
Length m 1.08
Width m 1.08
conditions. (One way of further use is a biogas digester.) The sludge accumulates in
the funnel-shaped bottom of the sedimentation tank (Table 8).
For particularly reed bed filtration system, holding or settlement tank is intro-
duced for collection and storage purpose of domestic wastewater (gray water). The
length, width, and depth of holding tank is 1.08, 1.08, and 0.6 m, respectively. The
capacity of holding tank is 700 L/day.
Design Criteria of Reed Bed (Horizontal) Filter System
Parameter Unit Value

Supply of drinking water LPCD 40
Total population Persons 30
Population for 1 unit Persons 15
Black water generation LPCD 10
Gray water generation LPD 22
Total gray water generation for 1 unit L/day or m3/day 330 or 0.33
Design of Organic Removal
Ct ¼ C0 ekt
where
t = function of bed area
QðlnC0 lnCt Þ
A¼
K BOD
where
A = bed area, m2
Q = avg. flow, m3/day
C0 = inlet 5-day BOD, mg/L
Ct = outlet BOD5, mg/L
KBOD = BOD5 reaction constant day 1
Design Specification Reed Bed (Horizontal) Filter System

Avg. influent BOD (considered) mg/L 80
Expected effluent BOD mg/L 10
KBOD Per day (0.17–0.18 recommended in India) 0.18
Bed area (A) m2 3.812309 or 4
BOD load mg/day or g/day 26,400 or 26.4
BOD loading on bed g/m2/day 6.6
Source: Arceivala and Asolekar (2005; page no: 283)
Hydraulic Consideration in Design

1. Hydraulic gradient is equivalent to slope of 5%.
2. Hydraulic conductivity will stabilize at around 1 103 m/s (86.4 m3/day) as
reed bed fully established.
3. Ac ¼ dH Q
Kf =dS Þ 86400
Ac = 0.076389 m2
where
82 P. K. Roy et al.
Ac = cross-sectional area of bed, m2

Q = 0.33 (avg. flow, m3/day)
Kf = 0.001 (hydraulic conductivity, m/s)
dH/dS = 0.05 slope, m/m
Design Parameter of Reed Bed (Horizontal) Filter System

Cross-sectional area of bed m2 0.076
Bed width (depth of bed recommended 0.6–0.9 in India so 0.6 m considered) m 0.127
Total bed area needed m2 4
Bed length m 31.496
According to desired aspect ratio (width/length) of 3:1–5:1 without altering the

total plan length 4 m and width 1 m
Detention time (net pore vol. m3/flow rate m3/day) = 4.24 or 5 days
where porosity of bed 30–40% recommended in India, so avg. porosity consid-
ered as 0.35 for typical ranges 2–5 days.
Hydraulic loading rate = (total grey water generation/cross-sectional area of
bed) = 4.342 m/day or 434 cm/day
Free board = 0.4 m
(Hydraulic loading rate must not exceed hydraulic conductivity of bed.)
Results of Physicochemical Parameter
See Table 9.
Percentage (%) of Removal Efficiency of Physicochemical Parameter

of Final Treated Effluent
See Table 10.

In reed bed filter system, BOD, COD, TKN, NH4-N, NO2, PO4, MPN (TC; FC),
and TSS removal efficiency (Table 10) are 84–79.29%, 88.23–89%, 55.36–56.28%,
74.77–99.02%, 55.56–84.2%, 74.0–76.87%, 97.57–98.92%, 99.99%, and
86.95–93.18%, respectively. And 3 no of Typha latifolia (Cattail) plants implanted,
after five (05) months, it is observed that 13 no of plants are harvested from those
plants. And plant growth rate (Table 11) also increased to 89 cm (from 6 to 95 cm) in
12 days, so it was observed that plant can survive and growth rate is also significant.
From this wastewater treatment process, it is noticed that BOD, COD, TSS, TKN,
NH4-N, NO2, PO4, TC, and FC removal efficiency is more than 80–90% avg. that
have been achieved of treated effluent of domestic wastewater (gray water). Result of
7-day study of heavy removal from wastewater using reed bed filtration system
3
Table 9 Results of Physico-Chemical Parameter

BOD3 COD DO NH4-N NO2 NO3 PO4
Sample pH (mg/l) (mg/l) (mg/l) TKN (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (TC,FC) MPN TSS
Raw 7.4–7.42 40–42.5 80–102 0 14.34–16.24 14.34–14.67 0.19–0.27 0–0.03 14.7–15.4 14*103; 44–46
water 14*103–33*106;
(influent) 33*106
Treated 7.46–7.48 6.4–8.8 8.8–12.0 1–3.2 6.4–7.1 1.0–3.7 0.03–0.12 0.8–0.9 3.4–4.0 150;340–700;630 3–6
effluent
Decentralized Integrated Approach of Water and Wastewater Management. . .
83
84
Table 10 Percentage (%) of Removal Efficiency of Physoico-Chemical Parameter of Final Treated Effluent
Sample BOD COD TKN NH4-N NO2 PO4 (TC;FC) TSS
Removal efficiency of 84–79.29 88.23–89 55.36–56.28 74.77–93.02 55.56–84.2 74.0–76.87 97.57–98.92; 86.95–93.18
treated effluent 99.99–99.99
Where flow rate is 10–20 L/day
P. K. Roy et al.
Table 11 Growth rate of a single plant

Day 1 2 3 4 5 6 7 8 9 10 11 12
Height of plant (cm) 6 19 30 40 45 50 60 67 73 82 86 95
Growth rate of Typha latifolia (Cattail) plant
Table 12 Removal of heavy metals

Cadmium Total chromium Arsenic Nickel
Parameter (Cd) (mg/L) (Cr) (mg/L) (As) (mg/L) (Ni) (mg/L)
Raw 6.0 6.0 0.6 9.0
Final treated effluent 0.714 0.57 0.15 1.29
Percentage (%) 88.10 90.5 74.86 85.66
removal efficiency
After 7 days of dosing
showed (Table 12) that cadmium (Cd), total chromium (Cr), arsenic (As), and nickel
(Ni) are 88.10%, 90.5%, 74.86%, and 85.66%, respectively. So, reed bed filter can
effectively remove heavy metal (74–90.5% avg.) also using plant absorption
process.
Result and Discussion
According to the 5-years rainfall data (India Meteorological Department, Govt. of

India) of the project area, the annual avg. rainfall is 1400 mm, and annual avg. wind
speed is 2.64 m/s which are relevant for the structure and surface water treatment
system. The water bodies’ water quantity potential and other water quality parameter
ponds are categorized, and pond no 9 is finally selected as a surface water source.
The length and breadth are 60 and 32 m, respectively, and wetted area is 920 m2. And
the catchment area is required 20,300 m2 for 28 KLD water treatment purpose.
Surface runoff water comes out from projected catchment area, and first, it is
stored into silt trap for sedimentation purpose. TSS of surface runoff water is 1 mg/L
and high-sediment load, and it was estimated that 2.64 m3/year (wet basis) sludge
volume was generated into silt trap from surface runoff water. For this reason silt trap
constructed before passes the surface runoff water into pond which is very effective
for sedimentation purpose.
The basic treatment process for the drinking water consists of horizontal roughing
filters, slow sand filters (HRF/SSF), and activated carbon filter with modifications to
established concepts with recent research results. Using this treatment system,
92–94% turbidity removal is possible from HRF 1 and 2 and 99.22% turbidity
removal is also possible from SSF1 and 2. And pH and DO are reduced from the
treatment system.
Reed bed filtration system is used for wastewater treatment system; the efficiency
of the system showed that 80–90% removal efficiency achievement is possible for
86 P. K. Roy et al.
following parameters BOD, COD, TSS, TKN, NH4-N, NO2, PO4,TC, and FC, and it
also removes 74–90.5% various heavy metals (Cd, As, Tot. Cr, Ni) using
bio-adsorption process.
Conclusion
A technical feasible, low-cost integrated, socially acceptable, and combined

decentralized eco-friendly solution has been elaborated with the treatment efficiency
of surface water treatment using silt trap and catchment area composite system,
respectively, and reed bed filtration system for wastewater treatment purpose which
are really applicable for arsenic-affected areas in rural India. The surface water is
treated by aeration, horizontal roughing filter, slow sand filter, activated carbon filter,
and post chlorination with optimum dosages. In addition also wastewater could be
treated using an eco-friendly technique like reed bed filter. This type of integrated
water and wastewater treatment system if established may provide an alternative
source of drinking water where sufficient pond systems exist under deteriorated
groundwater quality condition, and also treated wastewater may be used for irriga-
tion and other purposes with zero discharge at the end of the day. The main
challenges of awareness and ownership by the community are overcome by involv-
ing all relevant groups of the community in the water committee and patiently
working out compromises which are supported by all water committee members.
The developed concept promises an overall sustainable eco-friendly operation and
maintenance regime. The performance efficiency also proved the scope of the pilot
as a best practice model for communities in areas with non-potable groundwater
sources.
Acknowledgments The authors are very grateful to the Department of Science and Technology,
Government of India, for EU-INDIA collaborative project under FP7 framework for sponsoring the
research project awarded to School of Water Resources Engineering, Jadvpur University, Kolkata.
Help and assistance for the implementation overall project during analysis of water testing and field
visit from the team of School of Water Resources Engineering, Jadavpur University, India, and
Adelphi Research, Berlin, Germany, is also acknowledged.
References
AIIH and PH (All India Institute of Hygiene and Public Health) (2007) Report of the task force on
formulating action plan for removal of arsenic contamination in West Bengal. Government of
India Planning Commission Yojana Bhavan, New Delhi
Arceivala SJ, Asolekar SR (2005) Wastewater treatment for pollution control and reuse. 3rd edition,
McGraw Hill Education (India) Private Limited, pp 283–284
Pal S, Roy PK, Banerjee G, Mazumdar A, Chakraborti R, Banik M, Majumder A (2015) Socio-
economic multi criteria analysis study on unhygienic sanitation system and finding techno-
logical options to mitigate the problems at Murshidabad District, West Bengal. In: 47th Indian
water works association conference proceeding. Kolkata
Pereira SP (2012) Removal of cyanobacteria by slow sand filtration for drinking water. J Water
Sanitation Hyg Dev 2(3):133–145
Roy PK, Majumder A, Banerjee G, Roy MB, Pal S, Mazumdar A (2015) Removal of arsenic from
drinking water using dual treatment process. Clean Techn Environ Policy 17:1065–1076
Roy PK, Pal S, Banerjee G, Majumder A, Chakraborti R, Banik M, Mazumder A (2016) Integrated,
sustainable and eco-friendly surface and groundwater management in arsenic affected rural area
of West Bengal, India. Int J Environ Eng 3(1):60–63
SWRE, JU (School of Water resources Engineering, Jadavpur University) (Eco-India) Report
(2012) D1.6, energy-efficient, community-based water- and wastewater-treatment systems for
deployment in India. pp 5–78
Wegelin M (1996) Surface water treatment by roughing filters. SANDEC, Duebendorf
Major Issues on Beneficial Utilization of
Solar Energy in India 4
Debanjan Sannigrahi
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Solar Power Potential in India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
India’s Energy Policies and Its Achievement in Solar Power . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
Technology for Solar Energy Harvesting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Issues and Challenges of Solar Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Cross-References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
Abstract
Solar energy is most commonly exploited in three ways: (a) photovoltaic
(PV) systems for electricity generation, (b) solar thermal power plants for
obtaining electricity and heat, and (c) solar thermal appliances for beneficial use
of thermal energy. In January 2015, the Indian Government expanded its solar
plans, targeting 100 GW of solar power by 2022 which will comprise 40 GW
rooftop and 57 GW through large- and medium-scale grid-connected solar power
plants. But various issues or challenges are to be addressed for achieving real
success in the solar energy sector in India. There will be great demand of land for
installing solar power instruments as well as power grid infrastructure. The
pressure for utilizing more cultivable lands is to be reduced by giving more
preference to rooftops, desert areas, wastelands, and inland water bodies. The
substances used for the production of solar panels include some of the harmful
heavy metals, some carcinogens, and hazardous materials. The disposal of broken
panels or life-expired panels as well as batteries used in a solar panel system
D. Sannigrahi (*)
Advanced Management Institute for Training and Achievement (AMITA),
Mumbai, Maharashtra, India
e-mail: amita.m2t@gmail.com; debanjan.publication@gmail.com

https://doi.org/10.1007/978-3-319-73645-7_6
90 D. Sannigrahi
needs special attention to nullify the harmful effect of these wastes to the living
population and the environment. More focus should be given on research for
using recyclable, less hazardous, and more efficient materials in preparing solar
panels. The size and weight of solar PV module are to be reduced for making it
sustainable in cyclonic and coastal areas. The actual life span of solar panels
found in India is only around 7 years against the claim of 30 years since the
durability of a solar panel depends on its location and placement, extreme
weather, environmental conditions, and also on type and frequency of mainte-
nance. The life span of solar panels has to be enhanced for creating interest among
the investors/users. Dust deposition, bird droppings, or tree leaves accumulation
on solar panels reduce the efficiency up to 50%, if not cleaned properly at least
thrice a week and washed once a month. A quite good maintenance of solar panel
is essential in most of Indian locations. Washing with unfiltered or well water may
create unwanted water spots on panels and corrosion in aluminum frames of the
panels, thus reducing the efficiency. Covering the panels with a transparent screen
impregnated with transparent indium tin oxide electrodes (self-dusting Martian
technology) allows the removal of dust from solar panel. The unreliability in solar
power production due to short- or long-time power fluctuation and frequency or
voltage fluctuation caused by bad weather or less availability of solar radiation
creates a challenging task to integrate into power grid. The smart power balance
facility is essential for integrating solar energy sources with energy storage unit.
The momentum of large-scale utilization of solar energy can only be sustained if
it is backed by indigenous R&D, innovation, and manufacturing capability.
A close collaboration between the research community and the industry is vital.
Government encouragement, various subsidies, and assured power purchase
agreement will play a decisive role for making India the largest solar power
market in the world. More usage of solar energy is the best solution to drastically
reduce emission of both greenhouse and toxic gases in the environment.
Keywords
Environment pollution · Grid integration · Indian solar energy policies ·
Jawaharlal Nehru National Solar Mission (JNNSM) · Solar energy issues · Solar
photovoltaic systems · Solar power · Solar thermal system · Renewable energy
Introduction
The power sector is the most important sector for any country contributing sig-
nificantly in economic growth, rapid industrialization, smart urbanization, and
improvement of living standard of society. At present India is ranked fifth in
electricity generation, having aggregate capacity of 329.23 GWs out of which
66.7% (219,490 MW) is from thermal, 14.9% (44,653 MW) from hydro, 2.1%
(6780 MW) from nuclear, and about 17.7% (58,303 MW) from renewable energy
sources (as on August 2017) (Fig. 1). Although over the years, the Indian power
sector has experienced a quantum jump from its installed capacity of
4 Major Issues on Beneficial Utilization of Solar Energy in India 91
Fig. 1 Installed capacity and Nuclear

share of power plants in India
Biomass
Solar 2.1% 2.5%
(Source: http://powermin.nic.
in/en/content/power-sector-
3.9%
glance-all-india) Wind
9.9%
Hydro
14.9%
Thermal
66.7%
30,000 megawatt in 1981 to over 3 lakh 29,000 megawatt by August 31, 2017,
registering compound annual growth rate (CAGR) of 8.52% in the last 10 years, but
still there is a huge gap in generation and demand of electricity in India. Rachit and
Vinod (2016) mentioned about 3.6% shortage in energy and 4.7% shortage in peak
power (Table 1). Since availability of affordable energy is critical for both growth
and development of India, there is an urgent necessity to fill up this gap by
establishing more generation plants preferably using renewable sources for reducing
both import dependence on fossil fuels as well as emission intensity of greenhouse
and toxic gases and for providing eco-friendly healthy clean energy. Central gov-
ernment, state governments, and private sectors are participating in more and more
electricity production. Their share has been given in Table 2. Even though renewable
energy is an important part of India’s energy planning process, but still electricity
production of India heavily depends on coal, the dirtiest hydrocarbon fuel, which
contributes to about 58.8% of total energy generation. Source-wise estimated poten-
tial of renewable power in India as on 31 March 2016 is given below in Fig. 2. Solar
power has the maximum potential (62%) followed by wind power (34%). As per
Energy Statistics 2017 report, the geographic distribution of the estimated potential
of renewable solar power as on 31 March 2016 reveals that Rajasthan has the highest
share of about 14% (167,276 MW), followed by Gujarat with 13% share
(157,158 MW) and Maharashtra with 10% share (119,893 MW) (Fig. 3).
Solar Power Potential in India
India, being located in the northern hemisphere (between 8 4 and 37 60 N latitudes
and 68 7 and 97,0250 E longitudes) and divided into almost two equal halves by the
Tropic of Cancer (23 300 N), experiences 250–300 sunny days per year and receives
an average hourly radiation of 200 MW/km2. The southern part of India lies in the
tropical zone, while the northern part belongs to subtropical zone. It has the
estimated potential to generate 750 GW solar power assuming only 3% wasteland
92 D. Sannigrahi
Table 1 The requirement Energy in MU Peak power in MW

and availability of
Availability 1,030,785 141,160
electricity in India
(as on March 2015) Requirement 1,068,923 148,166
Shortage 38,138 7006
Percentage shortage 3.6 4.7
Source: Central Electricity Authority, Load generation Balance report
2015–2016
Table 2 Total installed Sector MW % of Total

capacity sector-wise
State sector 81,652 24.8%
(As on 08 March 2017)
Central sector 102,933 31.3%
Private sector 144,641 43.9%
Total 3,29,226
Source: Central Electricity Authority (CEA) http://powermin.nic.in/en/
content/power-sector-glance-all-India
Fig. 2 Source-wise estimated

potential of renewable power Small Hydro
in India as on 31 March 2016 Power,
(Source: http://www. 44%
Solar, 62%
indiaenvironmentportal.org.
in/files/file/Eneigy_Statistics_
2017.pdf)
Other, 4%
Biomass Power,
39%
Wind Power,
34%
Cogeneration-
bagasse 11%
Waste to Energy,
6%
Fig. 3 State-wise estimated Andhra Pradesh

potential of renewable power Uttar Pradesh 8%
in India as on 31 March 2016 2% others **
(Source: http://www. Telangana 14% Gujarat
indiaenvironmentportal.org. 2% Himachal
13%
in/files/file/Energy_Statistics_ Tamil Nadu
Pradesh
2017.pdf) 6%
3%
Rajasthan Jammu &
14% Kashmir
10%
Odisha Madhya Karnataka

3% Pradesh 8%
Maharashtra
7%
10%
is made available. The latest update as released by the National Renewable Energy
Laboratory (NREL), New Delhi, in February 2016 on the basis of 10 km resolution
solar resource maps for India shows the annual average direct normal irradiance
(DNI) across India, which illustrates that most areas of the country have greater than
5 kWh/m2/day of DNI (Fig. 4). This map shows that although the highest annual
radiation is received in Gujarat, Rajasthan, and the high-elevation Himalayan region,
the parts of Andhra Pradesh, Maharashtra, and Madhya Pradesh also receive fairly a
large amount of radiation as compared to many parts of the world especially Japan,
Europe, and the USA where development and deployment of solar technologies are
maximum (Amita and Soni 2011). Table 3 represents month-wise solar radiation
data of seven important cities in India situated at different latitudes indicating better
Average annual sum (2005-2010) 0 100 200 km
< 1250 1400 1550 1700 1850 2000 2150 > kWh/m2
Fig. 4 Solar resource in India (Source: https://www.nrel.gov/international/ra_india.html, 2017)

94 D. Sannigrahi
Table 3 Solar radiation data for seven cities in India having different latitudes (k Wh/m2/month)
Ahmedabad Delhi Jodhpur Kolkata Madras Srinagar Vizag
Month (L-23.07) (L-28.58) (L-26.3) (L-22.65) (L-13.0) (L-34.08) (L-17.22)
January 6.80 5.95 6.31 6.86 8.22 5.07 7.58
February 7.96 7.25 7.55 8.02 9.10 6.47 8.60
March 9.33 8.83 9.05 9.36 10.01 8.26 9.73
April 10.55 10.36 10.45 10.56 10.64 10.08 10.64
May 11.26 11.36 11.33 11.25 10.85 11.37 11.08
June 11.50 11.74 11.65 11.48 10.85 11.89 11.17
July 11.41 11.58 11.52 11.39 10.86 11.67 11.16
August 10.89 10.82 10.86 10.89 10.37 10.66 10.87
September 9.85 9.46 9.63 9.87 10.31 9.00 10.13
October 8.43 7.77 8.05 9.47 9.43 7.05 8.99
November 7.11 6.29 6.63 7.14 8.46 5.43 7.85
December 6.47 5.60 5.96 6.54 7.97 4.69 7.29
Source: Solanki (2011)
availability of radiation throughout the year and bright prospect of solar power
generation in India (Solanki 2011).
Climate change, deteriorating air quality, its negative impact on health, and subse-
quent urgency for shifting to cleaner and sustainable energy consumption are major
concerns for policy makers in every country. Gulati et al. (2016) narrated excellent
achievement on renewable energy sector by important European nations. Portugal
made history by working only on renewable energy (solar, wind, and hydro) for 107 h
from 7 to 11 May 2016. In the UK generation of solar energy (29 GWh) surpassed
energy generation from coal power stations (21 GWh) on 9 April 2016. In Germany
renewable sources of energy produced 87% of the total energy consumed on 8 May
2016. Solar photovoltaic (PV) systems accounted for more than 7% of the electricity
demand in Germany, Italy, and Greece during 2015–2016. India has also substantially
made progress in solar power capacity achievement since 2008. It has improved solar
energy production about 8 GW by July 2016 from the level of 3 MW in 2008–2009.
The cross-country comparison of solar power installed capacity and targets data as
presented in Table 4 shows that Germany is leading the show with 38.2 GW installed
capacity followed by China and Japan. The progress of China in the solar energy
sector is spectacular since in 2013 and 2014 China added over 21.6 GW solar power
systems followed by Japan 16.7 GW and the USA 10.5 GW (Gulati et al. 2016). Much
emphasis on solar power has also been given in India mainly due to following reasons:
(a) sunshine is a freely available, abundant, and nonpolluting source, (b) India has
tremendous potential to produce about 748 GW solar power, (c) solar power has an
advantage to electrify remote villages where power grid lines are absent or difficult to
reach or suffer from sporadic supply, (d) solar power is financially viable with falling
cost of production for industrial and commercial consumers, (e) India has to cut down
carbon dioxide and other greenhouse gas emission to bring it back to 2005 level, and
(f) solar power sector generates huge employments.
Table 4 Cross-country comparison of solar power installed capacity and targets in 2014
Installed capacity Target (year) CAGR (%) needed to meet
Country (GW) (GW) targets
Canada 1.7 6.3 (2020) 24
China 28.2 100 (2020) 23
France 5.7 15 (2020) 17
Germany 38.2 52 (2020) 5
India 3 100 (2022) 55
Italy 18.5 23 (2017) 7
Japan 23.3 65.7 (2020) 19
Thailand 1.3 3 (2021) 12
United 5.1 7.2 (2020) 6
Kingdom
Source: Bridge to India (2015), http://www.bridgetoindia.com/reports/india-solar-handbook-2015
India’s Energy Policies and Its Achievement in Solar Power
As a part of a climate action plan, India has committed to reduce emission intensity
by 33–35% by 2030 over the 2005 levels by boosting clean (renewable) energy in
electricity generation to 40% and adding carbon sinks (tree and forest cover) to
remove carbon dioxide from the atmosphere amounting to 2.5–3 billion tons of CO2
(Mohan 2015b). India’s per capita emissions is about 2.44 t/year in comparison to
China’s 8.13 t/year. In absolute emissions, India is the world’s 3rd largest polluter
after China and the USA, but its per capita emission is 1/8 of the USA and less than
1/3 of China. Every 1 GW of additional renewable energy capacity reduces CO2
emissions by 3.3 million tons per year.
Several electricity policies have been taken by India for promoting renewable
energy and for reducing fossil fuel energy. “Electricity Act 2003” encouraged for
generation of electricity from renewable sources by de-licensing stand-alone gener-
ation and distribution system. The increase in share of electricity from non-
conventional sources and its purchase by distribution authorities were advocated in
“National Electricity Policy 2005.” As per “National Rural Electrification Policy
(NREP) 2006,” access to electricity to all households was made compulsory with
quality and reliable power supply at reasonable rates. It gave guidelines for the
implementation of off-grid solar applications. This helped to generate only 33.8 MW
(as on 14 February 2012) solar power mainly in the form of solar lanterns, solar
pumps, home and street lighting systems, etc. The “Generation Based Incentive
(GBI) scheme” announced in January 2008 introduced feed-in-tariff (FIT) system at
the rate of Rs. 15/kWh for promoting grid-connected solar power plants which was
further modified with introduction of “National Solar Mission (NSM)” in 2008 as a
part of “National Action Plan for Climate Change (NAPCC).” NSM helped to
increase the share of solar power to 190 MW in 2011. The “Jawaharlal Nehru
National Solar Mission (JNNSM)” launched on 11 January 2010 has established
the national-level policy framework for solar energy utilization including power
generation in India. It has set following targets: (i) deployment of 20,000 MW grid-
96 D. Sannigrahi
connected solar power by 2022, (ii) 2000 MW of off-grid solar applications includ-
ing 20 million solar lights by 2022, (iii) 20 million square meter solar thermal
collector area, (iv) creation of favorable conditions for developing solar manufactur-
ing capability in the country, and (v) making India a global leader in solar energy
following required R&D. The mission has adopted a three-phase approach, spanning
the remaining period of the Eleventh Plan and the first year of the Twelfth Plan (up to
2012–2013) as phase I, remaining 4 years of the Twelfth Plan (2013–2017) as phase
II, and the Thirteenth Plan (2017–2022) as phase III. Targets of solar power systems
to be achieved in three phases are mentioned in Table 5. In January 2015, the Indian
Government expanded its solar plans, targeting 100 GW of solar power by 2022
which will comprise 40 GW rooftop and 57 GW through large- and medium-scale
grid-connected solar power plants. It is expected to abate over 170 million tons of
CO2 during its life cycle.
India quadrupled its solar power generation capacity from 2650 MW on 26 May
2014 to 10,000 MW on 10 March 2017. A team of engineers from the Indian
Institute of Technology (IIT), Bombay, led by the author, trained around 780 people
belonging to different villages across the country, with the help of NGO groups of
24 districts for assembling and repairing LED-based Solar Urja Table Lamps
designed and developed by IIT Bombay and distributed 7,35,352 lamps prepared
by those trainees to rural students of Madhya Pradesh, Rajasthan, Odisha, and
Maharashtra at a subsidized rate of Rs. 120 per lamp during December 2013 to
January 2015 under right to light to every child policy. Those students got the
freedom to study at night under the kerosene gas-free indoor atmosphere (Sannigrahi
and Kala 2016). During 2015 only, 118,700 solar home lighting systems were
installed, 1 million solar lanterns had been sold, 46,655 solar street lighting instal-
lations were provided, 30,256 solar-powered water pumps for agriculture and
drinking water had been installed, and 1.4 million solar cookers were distributed
or sold in India (MNRE 2016). The government of India is promoting the use of
solar energy through various strategies such as enhancement of budget allocation for
Jawaharlal Nehru National Solar Mission every year, establishment of a clean energy
fund, custom duty reduction and excise duty exemption on solar panels for private
solar companies, and initiation of Renewable Energy Certificate (REC) scheme for
driving investment in low-carbon energy projects.
Table 5 Targets of solar power system to be installed set by JNNSM

Target for Target for Target for Cumulative
phase I phase II phase III target
Application segments (2012–2013) (2013–2017) (2017–2022) (2012–2022)
Grid solar power includes 1100 MW 2900 MW 16,000 MW 20,000 MW
rooftop and small solar
projects
Off-grid solar applications 200 MW 800 MW 1000 MW 2000 MW
include rural solar lights
Solar collectors 7 million m2 8 million m2 5 million m2 20 million m2
Sharma et al. (2012) summarized India’s major achievements on solar energy

development as follows.
• Electrification of 3600 remote villages/hamlets, including those in Sunderbans,

Bastar, Ladakh, and the North East through solar energy
• Setting up of largest solar steam cooking system for feeding to 15,000 persons/
day by Tirumala Tirupati Devasthanams (TTD) at Tirumala
• Installation of solar water heating systems at 7 lakh m2 collector area
• Export of 30 MW capacity solar photovoltaic products to various developed and
developing countries
• Creation of solar energy center set up at Gurgaon in Haryana for development of
solar energy systems and devices
• Designing of a new architecture for the 1000 MW projects
• Fixation of tariff for photovoltaic (PV) system (Rs 17.91 per unit during 2012)
and for solar thermal power system (Rs. 15.31 per unit during 2012). NTPC
Vidyut Vyapar Nigam (NVVN) permitted new grid power projects of 620 MW
capacities.
Besides those mentioned above, the Ministry of New and Renewable Energy has
also launched a Scheme on “Development of Solar Cities”: 8 “Model Solar Cities,”
15 “Pilot Solar Cities,” and 14 “Green Campus.” As on 15 September 2015, Nagpur,
Chandigarh, Gandhinagar, and Mysore have been identified/sanctioned for Model
Solar Cities, 13 cities, namely, Agartala, Coimbatore, Rajkot, Shimla, Faridabad,
Thane, Raipur, Shirdi, Leh, Aizawl, Puducherry, Vijayawada, and Amritsar are
being developed as pilot solar cities and sanctions have been given for 14 campuses,
namely, Silver Jubilee Campus of Pondicherry University; Auroville Campus
(Puducherry); Dayalbagh Nagar Panchayat; School of Planning and Architecture
(New Delhi); Malkapur Nagar Panchayat; KIIT University; Tezpur University;
Indian Institute of Engineering, Science and Technology (BESU); Jadavpur Univer-
sity; Writers’ Building (Kolkata); Madan Mohan Malaviya University of Technol-
ogy (Gorakhpur); Orissa University of Agriculture and Technology (Bhubaneswar);
Shri Hanuman Vyayam Prasarak Mandal (Amravati); and National Institute of
Technology (Hamirpur) to be developed as Green Campus (MNRE 2015).
Cochin International Airport (Kochi Airport) has become the first airport in the
world that completely operates on solar power. The 12 MWp solar power plant
comprising 46,150 solar panels laid across 45 acres near cargo complex to produce
50,000–60,000 units of electricity per day. More airports across the country are
taking now the greener route. The Netaji Subhash Chandra Bose International
Airport in Kolkata is set to have a 15–20 MW solar energy capacity unit for taking
care of 60% of the airport’s power needs. The Jaipur airport, where a 100 kW rooftop
solar project is already running, is planning to install a 1.8 MW ground-based power
project. The Airports Authority of India (AAI) has announced that major airports in
the state of Rajasthan such as Bikaner, Jaisalmer, and Jodhpur will also set up solar
power plants for meeting a part of their daily power needs. Delhi’s Indira Gandhi
International (IGI) Airport and Bangaluru’s Kempegowda International Airport have
98 D. Sannigrahi
also started solar power project. As a part of its “Green Campus” initiative, Indian
Institute of Technology Bombay (IIT Bombay) installed a 1MWp (1 MW peak PV
power) distributed rooftop solar PV power plant on the roofs of its 16 academic
buildings. The plant occupies approx. 12,000 m2 area on the rooftops and supplies
up to 50% of peak load demand of 16 academic buildings. Dayalbagh Educational
Institute (DEI), Agra, is connected to the electrical grid with its 520 kWp photovol-
taic unit since 2012 and utilized solar-based electricity. Usually, there is enough
electricity being produced by the power plant to meet the load of the institution as
well as to feed the houses in Dayalbagh colony with their surplus power. Defence
Research and Development Organisation (DRDO) has established its research
station at an altitude of 17,500 ft at Chang La in Ladakh, by introducing a new
technology for solar-heated shelters for their use at extreme altitudes (Mohan
2015a).
Technology for Solar Energy Harvesting
Solar energy is radiant light and heat from the sun harnessed using a range of ever-
evolving technologies such as solar heating, photovoltaic, solar thermal energy,
solar architecture, artificial photosynthesis, etc. Solar energy is most commonly
exploited in three ways: (a) photovoltaic (PV) systems for electricity generation,
(b) solar thermal power plants for obtaining electricity and heat, and (c) solar
thermal appliances for beneficial use of thermal energy. Photovoltaic cells, being
semiconductor devices, convert part of the incident solar radiation directly into
electrical energy. Solar PV cells are available as crystalline silicon cells [single-
crystalline silicon (sc-Si) and multi-crystalline silicon (mc-Si)], amorphous silicon
cells [thin films of amorphous and micromorph silicon (a-Si/μc-Si), Cadmium –
Telluride (CdTe) and Copper-Indium-Diselenide (CIS) & Copper-Indium-Gal-
lium-Diselenide (CIGS)], dye sensitized solar cells (DSSC), Silicon nano particle
ink cells, Carbon nanotube (CNT) and Quantum dots cells. Commercial efficien-
cies of these solar photovoltaic modules are given in Table 6. Phani et al. (2001)
described about Titania solar cells which were able to convert sunlight directly into
electricity through a process similar to photosynthesis and had performance
advantages over other solar cells. In case of concentrator photovoltaic (CPV)
Table 6 Commercial efficiencies of photovoltaic modules

Type of PV cell (market Wafer-based crystal Thin films
representation) silicon (85–90%) (10–15%)
Cell material sc-Si mc-Si a- CdTe CIS/
Si/μc-Si CIGS
Current conversion 15–20% 15–17% 6–9% 9–11% 10–12%
efficiency
Source: Sharma (2011)
technology, an optical solar concentrator system is used to focus solar radiation

onto a small but high-efficiency cell (Sharma 2011). Either mirrors or lenses are
used to concentrate the solar energy for a CPV system. Solar concentrators are
often mounted on a solar tracker in order to keep the focal point upon the cell as the
sun moves across the sky. The magnitude of generated electric current depends on
various factors such as the exposed area of the solar cell, intensity of the solar
radiation, ambient temperature, and fabricating material of solar cell. SPV module
is made by joining solar cells in series and parallel combinations. The performance
of solar PV measured as capacity utilization factor (CUF) depends on several
factors including the solar radiation, temperature, air velocity apart from the
module type and quality, angle of tilt or tracking, design parameters to avoid
cable losses, and efficiencies of inverters and transformers (Sharma 2011). Thin-
film modules perform better than the crystalline modules in high-temperature
zones.
In solar thermal power systems, solar radiations are concentrated using con-
centrating solar collectors such as mirrors and reflectors. This focused radiation
produces heat which is carried by thermic fluids for producing steam or hot gases,
which are then used to drive heat engines or turbine and to produce electricity. These
thermal plants are based on four basic essential systems such as collector, receiver
(absorber), transporter/storage, and power converter (Sharma 2011). Commercially
available technologies include use of parabolic trough-shaped mirrors, central
receiver-mounted solar towers, parabolic-shaped dishes for tracking sunlight, and
use of linear Fresnel reflectors (Fig. 5). The output from the solar thermal plant
depends on design parameter, and performance is measured by measuring capacity
utilization factor (CUF).
Different solar thermal appliances like domestic solar water heater, solar
cooker, solar oven, solar distilled water plant, etc. are made for beneficial use of
heat of sunshine in houses. Similar to greenhouse effect, heat of sunshine are
captured and used for drying, cooking, or heating water at household level. An
innovative approach made these items sometimes foldable, portable, and adjustable
to the sun’s direction for better efficiency.
Issues and Challenges of Solar Energy
The disadvantages of solar energy are (a) its unreliability due to weather depen-
dency, (b) non-generation during peak load needed in the evening or in nights, and
(c) mostly dependent on costly storage battery and inverter. But it has also manifold
advantages like abundance, use in remote areas, nonpolluting, clean, efficient, no
noise pollution, and low maintenance. In the urban environment, modern PV
systems, which are architecturally integrated into buildings, are able to provide a
direct supply of clean electricity that is well matched to the demand of the building
but can also contribute significantly to daylighting and control easily the shading and
ventilation problem of house. There are many vital issues or challenges which need
to be addressed for achieving success in solar energy.
100 D. Sannigrahi
sunrays
Receiver
Absorber sunrays
Tube
Reflector
Solar Field
Piping
Heliostats
Tower
Parabolic Trough Central Receiver
Receiver / Engine
Reflector
Parabolic Dish / Engine Linear Fresnel reflectors
Fig. 5 Solar concentrating technology used for solar thermal power plants
Grid Connection for Rural Electrification

Both grid and off-grid connection are feasible in utilization of solar energy. Grid-
connected solar energy is advantageous for getting 24 h uninterrupted power supply
and lesser maintenance and running cost. Off-grid connection is also advantageous
for the people who desire for independence from the unreliable, fault prone, and
interrupted grid connection. In India government machinery is encouraging both
type of solar energy generation. But many people are staying in villages situated in
isolated remote areas and also in hilly terrains where transmission of electricity could
not be carried out due to difficult terrain and high transmission loss of electricity
from overhead wires. The lack of electricity infrastructure is one of the main hurdles
in the development of rural India. More than 18,000 villages cannot be electrified
through an extension of the conventional grid. Developments in cheap solar tech-
nology may be the potential alternative to distribute electricity by making local grid
infrastructure. Decision on type of connection, though place specific, is an important
issue for extending support/encouragement in the form of incentive and subsidies.
Grid integration for both small- and large-scale generation avoiding grid congestion
and problem related to weak grid in a vast country like India is a great technological
challenge. The unreliability in solar power production due to short- or long-time
power fluctuation and frequency or voltage fluctuation caused by bad weather or less
availability of solar radiation creates a challenging task to integrate into power grid.
The power balance using fast semiconductor switches and introducing real-time
computer controllers is essential for integrating solar energy sources with energy
storage unit.
Land Scarcity
Solar projects are known as “large space occupying projects” since solar energy
installations are directly linked to land for harvesting maximum sunshine. The
amount of land surface required for utility-scale solar power plants is approximately
1 km2 (250 acres) for every 20–60 MW electricity generation. Land is a scarce
resource in India and per capita land availability is very low (0.12 ha in 2014).
Dedication of land area for exclusive installation of solar arrays often must compete
with other necessities like agriculture, horticulture, urban development, industriali-
zation, road and rail construction, etc. that require land. Arrangement of required
land for 100 GW project is a tremendous challenge. Utilizing more and more
rooftops, desert areas, and wastelands will, no doubt, reduce the pressure from
utilizing the cultivable lands. However, the Ministry of New and Renewable Energy
(MNRE), Government of India, has stipulated and prioritized more use of barren and
wastelands for setting up of solar plants. In one side research is going on to achieve
greater efficiency in solar technology, while in other side, efforts are made to use
water surface area available on canals, lakes, reservoirs, and farm ponds for con-
struction of large-capacity solar power plants to reduce the huge demand of lands for
solar projects. As mentioned earlier vast unused vacant areas in airports are utilized
for placing solar PV modules in India. There is also a possibility to use highways and
railway tracks for installation of different types of solar power plants at a height of
nearly 10 m just to minimize transmission line costs and to avoid excessive cost of
land nearer to load centers. It will also protect the highways from damage due to
rain and intense summer heat and will provide additional comfort to commuters.
Utilization of rooftops for putting solar panel is another way to reduce the demand of
huge land requirement. Institutions and office buildings across India have sizable
place as rooftop which can provide considerable quantity of solar energy if fitted
with solar PV modules. Excess energy after their own consumption will be added
through grid for tackling other’s energy crisis. Reduction in energy demand by
institutions will help to tackle unavoidable power shortage, especially during day-
time. The advantages of rooftop solar power plant are (i) low gestation period,
(ii) saving in transmission and distribution losses, (iii) utilization of vacant rooftops
for power generation, and (iv) no requirement of additional land and amount toward
operation and maintenance, safety, security, etc. Maintenance and upkeeping will be
the responsibility of solar power generator, and thus government has not to pay
anything on this regard (Gupta 2014). During estimation of rooftop solar photovol-
taic potential of Mumbai city, Singh and Banerjee (2015) have observed that large-
scale deployment of this system can provide 12.8–20% of the average daily demand
and 31–60% of the morning peak demand for different months, even with median
conversion efficiency panels. They estimated a potential of 2190 MW solar energy
102 D. Sannigrahi
for Mumbai city with median efficiency panels at an annual average capacity factor
of 14.8%. Even in achieving Indian government’s ambitious target of 100 GW by
2022, government has given emphasis to achieve 40 GW from rooftop grid interac-
tive solar power and 60 GW from land-mounted grid-connected solar power (MNRE
2015). After availing central financial assistance (CFA) of 15%, the average cost of
grid-connected rooftop solar power systems comes down to Rs. 8.0 crore per MWp
capacity. Requirement of land can be reduced by making highly efficient solar cells/
panels and by following innovative approach of vertical placement of solar panels,
for which extensive and challenging research is required.
Durability (Life Span) and Performance of Solar Panels

The usual life span of solar panels is 30 years, but in India its practical life span is
found to be only around 7 years (Mishra et al. 2013). The durability of solar panels
depends on many delicate factors like location and placement of solar panels,
extreme weather and environmental conditions, type and frequency of maintenance
by skilled personnel, and quality of semiconductor material. Even though manufac-
turers offer guaranty period for about 20–25 years, but uncertainty on long-term
reliability of solar cells/panels due to above factors creates lack of interest in
marketing of panels among both dealers and consumers. Keeping high motivation
intact for a longer time among common people for installation and use of solar power
system is a challenging task. The power output rate degrades at about 0.5%/year due
to aging effect. Table 7 showed the analytical review on output loss of pre- and post-
2000 installation carried out by NERL indicating faster degradation of thin-film solar
panels in comparison to crystalline silicon-based panels (Maehlum 2014). The
possible reasons for degradation of solar panels are (a) the slow breakdown of
ethylene vinyl acetate (EVA)-made panel’s encapsulation and back sheet made of
polyvinyl fluoride films, (b) the gradual obscuration of the EVA layer between the
panel’s front glass and the cells themselves, and (c) the deterioration of solar cells
due to temperature increase (Sharma 2011). Panel’s encapsulation protects the cells
and internal electrical connections against moisture ingress. Sunlight slowly breaks
down the encapsulation materials through ultraviolet degradation, making them less
elastic and more plastic. Over time, the trapped moisture starts corrosion of the cell’s
electrical connections, resulting in the creation of higher resistance and decrease in
panel’s operating voltage. The discoloration of the EVA layer, due to interaction
Table 7 Output loss of pre- and post-2000 solar installation

Output loss (% per year)
Solar cell type Pre-2000 installation Post-2000 installation
Amorphous silicon (a-Si) 0.96 0.87
Cadmium telluride (CdTe) 3.33 0.4
Copper indium gallium selenide (CIGS) 1.44 0.96
Monocrystalline silicon (mono-Si) 0.47 0.36
Polycrystalline silicon (poly-Si) 0.61 0.64
Source: Maehlum (2014). http://energyinformative.org/lifespan-solar-panels
between cross-linking peroxides and certain stabilizing additives and also due to
oxidation of EVA layer, causes significant reduction in output of solar panel.
Exposure to sunlight creates defects in silicon cell by forming metastable dangling
bonds which capture electrons and reduce the electrical output. Johnston (2003) has
shown that creation of these dangling bonds leads to a 15–20% reduction in
efficiency. Effective research on solar cell materials is necessary for tackling this
degradation issue as well as increase in efficiency issue.
Performance of solar panels also depends on other important factors like panel
orientation, inclination angle, mounting position, and weight of panels. Since India
lies in the northern hemisphere with its southern tip quite close to the equator, panel
mounting should be done keeping its face on the south direction for receiving
maximum sunshine on PV cells with less reflection. In temperate zone the sun is
always toward the south, and in the tropical zone, it is predominantly in the south. If
there is any problem with the southern side, then the panel can be mounted by
keeping the face on 45 east or west of south. Tilt or inclination angle of panel with
respect to horizontal plane is another important parameter. For a fixed (non-tracking)
mounting, the maximum radiation can be obtained by tilting the surface at an
optimum angle, which is determined by the latitude of the location. The PV
efficiency is affected by the developed temperature inside the panel, usually decreas-
ing efficiency with increasing temperature. For fixed-type system, panels should be
mounted by keeping a space so that movement of air will not be restricted; otherwise
panels will be considerably hotter (up to 55 C at 1000 W/m2 of sunlight), affecting
its efficiency. Solar panel along with its mounting fittings is fairly heavy. In cyclone-
prone areas and in case of asbestos or other roofs, weight of PV panel poses safety
problems. The cyclones Aila and Phailin with wind speeds of 120–200 kph have
knocked down thousands of solar power systems in coastal Andhra Pradesh and
Odisha of India. Hence, the size and weight of solar PV module are to be reduced for
making it sustainable in cyclonic and coastal areas. Extensive research on new and
efficient design is the prime need for avoiding all those problems.
Water Requirement for Solar Power Systems

Desert offers excellent opportunity for harvesting solar energy. Dust deposition on
solar panel is acute problem along with water scarcity in desert area. Cleaning of
solar panel properly at least thrice a week and washing once a month are essential to
avoid reduction in efficiency of solar panels up to 40–50% in most of the Indian
locations (Deodhar 2010). A quite good maintenance of solar panel is essential in
India. Washing with unfiltered or well water may also create unwanted water spots
on panels and corrosion in aluminum frames of the panels, thus reducing the
efficiency further. Martian technology developed by NASA, USA, is a unique
solution to remove dust from solar panels. Covering the panels with a transparent
screen impregnated with transparent indium tin oxide electrodes allows the removal
of dust from solar panel. In this self-dusting technology, sensors monitor dust levels
on the surface of the panel and energize the indium tin oxide material when dust
concentration reaches a critical level. The electric charge sends a dust-repelling wave
cascading over the surface of the material, lifting away the dust, and transporting it
104 D. Sannigrahi
off of the screen’s edges. This process removes about 90% of dust deposited on the
panels within 2 min and requires only a small amount of electricity generated by the
panel for cleaning purposes (Quick 2010). The efficiency of a solar panel system gets
easily affected by the trees and shadow of the tall buildings and towers (both
electrical and communication) in the surroundings and even by the bird droppings
and tree leaves accumulation (Mishra et al. 2013). Shadows convert the affected
portion as insulator from conductor, and heat is developed causing sometimes
burning of that area and permanent damage to solar panel. Spraying with deionized
or filtered water is useful to remove dust, tree leaves, and bird droppings effectively
from solar panels. Solar thermal power plants require substantial water for its
operation. But it is interesting that availability of solar radiation is more in Rajasthan
where water is a scarce commodity. Technological breakthrough is necessary for
harvesting more solar energy with less water requirements.
Cost Economics of Solar Cell

Similar to any other business activities, cost economics is the crucial factor for
success and failure of any development project. Initially solar energy technology was
fully based on crystalline silicon, which was available from the electronic industry
and hence very costly. Monocrystalline silicon wafer is developed first by cutting the
ingots prepared from liquefied sand. Wafers are then used in making cells by
involving electrical circuit and layers of glass cover, antireflective quoting, etc.
(Gulati et al. 2016). Monocrystalline silicon is the most efficient on account of
highest degree of purity and hence most costly in comparison. Production of PV
panels is more labor intensive than capital and technology intensive. In India 60% of
production cost is for panel materials, while the remaining 40% is considered as soft
costs like installations, land acquisition, labor, inspection, transportation, etc. With
the rise in demand of PV panels globally, the demand for silicon by the PV industry
is increasing day by day and competing with demand of the electronic industry.
Situation has been reversed with increasing the dependency of the silicon industry on
solar industry and forced to reduce the price of silicon. The cost of PV panels has
fallen by more than 80% since 2008, which can be attributed to (a) fall in polysilicon
prices, (b) cost-reducing technological innovations, (c) fall in price of consumables,
and others. Even the use of silicon in solar cell has been reduced drastically from
15 g/W in 2000 to about 5.2 g/W in 2014 with introduction of new efficient
technologies. In India also, there is declining capital costs of solar PV projects,
about 68% since 2010–2011. Further decrease at the rate of 5–10% annually in cost
of solar panel in the global arena is expected in the next decade. It has a strong
influence on the price of solar power. Trend has taken an opposite turn now in India
with respect to conventional thermal power whose cost is increasing over years.
Compared with cost of thermal power Rs. 5.93/kWh, solar energy definitely has
gained much cost efficiency at present with Rs. 5.68/kWh tariff without accelerated
depreciation. Situation will be more impressive in the near future with the introduc-
tion of efficient but cheaper solar panels/modules.
Around 2008 China became the largest PV manufacturer globally by exporting
98% of its solar products. In 2014, China and Taiwan accounted for 69% of total PV
module production. The growth of the solar PV industry was very slow in India in
comparison to developed European countries and the USA. Currently, India’s
manufacturing and research capabilities are far below requirement. With the initia-
tives and encouragement of present Indian government led by Prime Minister
Narendra Modi, the future of India’s PV industry is looking very promising and
bright with capacity addition plans. Three Memorandum of Understandings (MoUs)
have been signed under “Make in India” program for changing the scenario in solar
energy arena. These are: (i) Adani and SunEdison signed an MoU to establish the
largest, vertically integrated PV-manufacturing facility in India; (ii) the Essel Group
and JA Solar, China’s leading solar energy firms, signed the agreement to launch a
solar cell and module manufacturing company as joint venture; and (iii) Welspun
Energy of India signed an MoU with Trina Solar of China to set up 500 MW pa solar
cell and module manufacturing facility in India (Sharda 2015). All these efforts will
help to bring solar energy revolution in India by creating better R&D facilities in
India and making cost-effective and efficient but lighter solar cells and modules.
Time has come for effective countering of the public perceptions that solar energy is
expensive and not feasible to meet evening demand.
Environmental Pollution and Health Hazard Issues

Solar energy, being clean energy, is free from environmental pollution as compared
to pollution-prone thermal energy. But the substances like arsenic, cadmium, and
polysilicon used for the production of solar cells and panels are either harmful heavy
metals or carcinogenic hazardous materials. During manufacturing each ton of
polysilicon produces four tons of liquid wastes which if exposed to the atmosphere
can get transformed into various harmful acids and gases (Mishra et al. 2013). The
factory workers busy in manufacturing solar panels are at the highest risk of health
hazards since they get exposed to the carcinogenic and toxic chemicals at a high and
frequent rate. After completion of life span, if solar panels are not properly disposed,
users including the local people of the surroundings will inhale health-hazardous
toxin leaking out from the disposed panels. Exposure to high concentration of
different hazardous material will cause various health problems such as selenosis
from selenium; damage of the brain, nervous system, kidney, etc. from lead; lung
cancer and chronic breathing difficulties with coughing, chest pain, etc. from
beryllium; damage of both the central nervous system and kidney from mercury;
various skin diseases with lung cancer and brain damage from arsenic; liver and
kidney damage with impaired immune system from trichloroethylene; damage to
kidney and bone density from cadmium; damage to the heart, liver, and spleen with
brain swelling, muscle weakness, and increased blood pressure from barium; hor-
monal interference with reproductive harm from brominated flame retardants;
immune suppression along with cancer and damage to the liver, nervous system,
and reproductive system from polychlorinated biphenyls; skin disorders, liver prob-
lems, and impairment of immune, endocrine, and reproductive system from dioxins
and furans; allergic reactions for asthmatic bronchitis and DNA damage from
chromium, etc. (Mishra et al. 2013). Careless approach during disposal of broken
panels and batteries will also create harmful effect to the living population and the
106 D. Sannigrahi
environment. More focus should be given on research for using recyclable, less
hazardous, and more efficient materials in preparing solar panels.
Removal of Uncertainties for Potential Investor

Besides government budget allocation, potential investors also play a vital role for
bringing success of any project. Investors show their interest if they find better
potential of the technology and good margin of profits by selling their products. In
case of solar energy, also potential investors can help the country by bringing
advanced and efficient technologies in manufacturing of PV modules. The German
and Japanese solar capacity additions have been driven by the feed-in-tariff (FIT)
policies. FIT is a policy mechanism designed to accelerate investment in renewable
energy technology. It offers long-term contracts to renewable energy producers,
typically based on the cost of generation of each technology. The US capacity
additions, on the contrary, have been driven by tax incentives (30% cash tax
break) and state-wise renewable purchase mandate (Sharda 2015). In India there
are uncertainties on nature of solar power, lack of grid parity and grid tariff, weak
finances of state discoms (the predominant buyer of solar energy), lack of stringent
solar renewable purchase obligation (RPO) mechanism, untested transmission net-
work and infrastructure, etc. All these uncertainties prohibit potential investor to
invest money in solar projects. All these issues must be addressed to attract investors,
which is a great challenge to the Indian Government.
Conclusion
India is a vast country both population and area-wise. Due to remoteness and
isolation in difficult hilly terrain, more than 18,000 villages in India are still deprived
of the advantages of electricity. Rural people with electric connections are facing
constant blackouts/power cuts, erratic voltage, and unreliable power supply. In this
electronics era, the communication system has reached even nooks and corners of
rural India where mobile charging is a vital requirement, television and other
electronic gadgets are essential commodity, and energy security is the priority area
for government. India, being bestowed with huge solar radiation, is in a favorable
position to reap the benefits of solar energy. Rooftop and off-grid facilities have
helped to generate electricity from solar panels even in remote and isolated areas in
India, which was not possible few years back considering the huge cost in construc-
tion of electricity supply line and tremendous transmission loss. Momentum of large-
scale utilization of solar energy can only be sustained if it is backed by indigenous
R&D, innovation, and manufacturing capability. A close collaboration between the
research community and the industry is vital and that has been started in an
aggressive mode. With the drastic fall in prices of solar modules combined with
rising prices of grid power, solar energy solutions are increasingly becoming viable
economically. The Government of India has given high priority to the renewable
energy sector with an allocation of Rs 1000 crore in its 2015–2016 budget for
development of ultra-large solar power plants and 25 solar parks in India.
Government encouragement, various subsidies, and assured power purchase agree-

ment will play a decisive role for making India the largest solar power market in the
world. Sincere efforts from both the government sector and private sector will help to
solve all important issues currently prohibiting growth of solar sector in India. Smart
grids and efficient energy storage system will help to maintain grid stability. India
has taken steps in the right direction.
Cross-References
▶ Global Environmental Issues

▶ Homeopathic Nanomedicines and Their Effect on the Environment
▶ Major Environmental Issues and Problems of South Asia, Particularly Bangladesh
▶ Photovoltaic Systems and Equipments for the Rural and Urban World
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Major Environmental Issues and Problems
of South Asia, Particularly Bangladesh 5
G. N. Tanjina Hasnat, Md. Alamgir Kabir, and Md. Akhter Hossain
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
Major Environmental Issues and Problems of South Asian Countries . . . . . . . . . . . . . . . . . . . . . . . . 112
Climate Change . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Climatic Events . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Geophysical Setting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Glacier Melt and Sea Level Rise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Land Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Water Scarcity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Ecosystems and Biodiversity Loss . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Import of Hazardous Wastes in South Asia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Country Basis Environmental Issues, Causes, Vulnerable Areas, and Overall Impacts . . . . . . . 116
Afghanistan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
Bhutan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
Maldives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
Nepal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
G. N. T. Hasnat (*)
Department of Land Administration, Faculty of Land Management and Administration, Patuakhali
Science and Technology University, Dumki, Patuakhali, Bangladesh
e-mail: gnthasnat@gmail.com
M. A. Kabir
Department of Agroforestry, Patuakhali Science and Technology University,
Dumki, Patuakhali, Bangladesh
e-mail: alamgirmk@gmail.com
M. A. Hossain
Institute of Forestry and Environmental Sciences Chittagong University, University of Chittagong,
Chittagong, Bangladesh
e-mail: akhter.hossain@cu.ac.bd

https://doi.org/10.1007/978-3-319-73645-7_7
110 G. N. T. Hasnat et al.
Pakistan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Sri Lanka . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Bangladesh . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Conclusion and Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
Abstract
South Asia covers diversified climatic zones and experiences an array of climate
change impacts. Human pressures together with changing hydrology and land
resources have distinct impact on the production of food grain and resilience of
ecosystems. The most threatened areas are grasslands and mountain forest eco-
systems of the Himalayas and ecosystems of the Sundarbans. Forests of South
Asia having most biologically diverse ecosystems on the planet are destroyed due
to rapid deforestation and urbanization. Moreover, the South Asia partake the
worst air pollution in the world, and it is maximum in India. Thar Desert is
extending at a rate of 100 ha per year which may cause damage to approximately
13,000 ha of cultivated lands and pastures in India and Pakistan. Availability of
freshwater is highly seasonal in this region, and water supplies become more
threatened by higher temperatures, changes in river regimes, and greater inci-
dence of coastal flooding. This article discusses major environmental issues faced
by the South Asian people particularly Bangladesh and the resultant problems
encountered by majority of people. Major environmental issues discussed here
are climate change, geophysical setting, ecosystem changes, overgrazing, import
of hazardous wastes, deforestation, desertification, pollution, population pressure,
collapse and pollution of land resources, water resources and lack of potable
water, biodiversity loss, food security risks, depletion of energy resources, and
degradation of river and marine resources. Different problems created by men-
tioned environmental issues like biodiversity loss, impacts to the marine envi-
ronment, atmospheric pollution, deficient urban structure, water scarcity and
degradation, soil erosion and land degradation, natural disaster, pests, and dis-
eases have been depicted in this chapter. Some recommendations have also been
provided on the basis of major environmental issues identified and resultant
problems.
Keywords
Afghanistan · Agrochemicals · Arsenic · Bangladesh · Bhutan · Biodiversity ·
Brickfield · Climate change · Cyclone · Deforestation · Desertification · Disease ·
Drought · Ecosystem · Exotic · Flash flood · Forest fire · Glacial melt · Global
warming · Greenhouse gas · India · Industrialization · Invasion · Land
degradation · Landslide · Lightning · Livelihood · Nepal · Pakistan · Pollution ·
Population pressure · Salinity · Sea level rise · Sedimentation · Shrimp
cultivation · Soil erosion · Sri Lanka · Sundarbans · Urbanization · Vulnerability ·
Waste · Water scarcity
5 Major Environmental Issues and Problems of South Asia, Particularly. . . 111
Introduction
South Asia is the large unique landmass representing the southern region of the
Asian continent. The South Asia comprises of eight countries – Bangladesh, India,
Nepal, Pakistan, Bhutan, Maldives, Sri Lanka, and Afghanistan (Sivakumar and
Stefanski 2010). The total area of South Asia covers almost 5.1 million km2 (1.9
million mi2), and this is 11.51% of the Asian continent. The land mass of this region
gives a ground for near 1.749 billion people that covers about one fourth of the
world’s population (SACEP 2016). South Asia is not only the most populated region
in the world but also densely populated (South Asia Regional Overview 2008).
The physiography of South Asia region ranges from the northern mountains to
southern plateaus. The landforms distributed from the world’s highest magnificent
Himalayas with nearly two dozen peaks rising to 24,000 ft or above of Bhutan and
Nepal to the lowest, the Bay of Bengal, the Indian Ocean, and the Arabian Sea
beaches. The physical landscape of this region is also demonstrated with the fertile
delta of Bangladesh, peninsula of India, and jewel-like islands of Sri Lanka and
Maldives in the Indian Ocean.
The South Asia is ecologically more valuable area in the world because of its
diversified natural resources and ecosystems. The total forest area of South Asia
covers 2.73% of world’s forests and provides a shelter for approximately 15.5%
flora and 12% fauna of the world. The floral diversity comprises 39,875 species of
flowering plants, 66 conifers and cycads, and 764 ferns. Faunal diversity is wide-
ranging with 933 species of mammals, 4494 birds, 923 reptiles, 332 amphibians, and
342 freshwater fishes. Only the Hindu Kush Himalayan belt was embracing a home
to a number of 25,000 major plant species that covers 10% of the world’s total flora.
In addition, India contains extensive savannah and forest habitats that provide spaces
for many endemic species having international importance. Sri Lanka is also one of
the most biologically diversified countries in the world. South Asia is the home of
around 14% of the world’s mangrove habitat. Moreover highest percentage of
threatened wetlands are in here, 82 of which are in Bangladesh.
The climate types of South Asia are quite difficult to understand and describe.
About half of the climatic zones that exist on the earth can be found in South Asia.
Though the climatic condition is quite different and varies considerably from area to
area as of tropical monsoon in the south to temperate in the north, several distinct
zones appeared here quite clearly. The total area is broadly separated into six main
climate zones. The highland zone has the coldest climate. This area covers the
Himalayas and other northern mountains. Snow exists here in all the year-round.
Another one is the humid subtropical zone, much warmer than the highland zone.
This zone includes the lower elevations and encompasses the deluxe slopes and
valleys of Nepal, Bhutan, and northern India and the Indo-Gangetic Plain.
The semiarid zone is a region of high temperatures and light rainfall. This type of
region is generally found at the western end of the Plain and in parts of the Deccan
Plateau. The other zone is the desert zone, and it covers much of the lower Indus
Valley in the borderlands of Western India and Southern Pakistan. The Thar Desert is
located in this region and is the driest part of this area with an average 10 in. annual
rainfall. The tropical wet zone is found along the western and eastern coasts of India
and in Bangladesh. Temperatures are comparatively high, and rainfall is heavy in
this zone and has recorded a world’s record of 366 in. in a month. The sixth one is
tropical wet and dry zone. In Sri Lanka the southern part has a tropical wet climate,
while the northern part reveals a tropical wet and dry climatic zone.
The variety in climatic conditions of South Asia mainly is influenced by three
bases – the altitude, vicinity to the seacoast, and the seasonal impact of the mon-
soons. Literary monsoon means seasonal winds that bring alternating periods of wet
and dry weather. During summer season winds blow from the sea and bring
moisture, called wet monsoon period. But, in the winter season winds blow out
from the center of the region toward the sea and bear much less moisture. This period
is dry monsoon period. The climate of South Asia is influenced by the monsoon
patterns. The southern parts are near to the seacoast, so it’s mostly hot in summer and
receive rain during monsoon periods. The northern belt of Indo-Gangetic Plains gets
both the seasonal warm air from the seacoast and the cold air of Himalayas. The
mountainous north is colder and receives snowfall at higher altitudes of Himalayan
ranges.
Although monsoons are crucial for South Asia, it causes severe suffering for
millions of people, especially in the lowlands of Bangladesh and India. Monsoons
are highly unpredictable, and recent years abnormal monsoon patterns generate more
frequent and intensive natural disasters as well as climate change.
Major Environmental Issues and Problems of South Asian

Countries
Having diversified climatic zones along with its physical landscape, the region
experiences a huge range of climate change impacts, for example – glacial melt,
sea level rise, soil erosion, saline water intrusion, etc. The key environmental issues
in broad aspect which are a great threat to the sustainable development of South Asia
are discussed below.
Climate Change
Climate change is the mother of all climatic hazards and extreme weather events,
such as heat waves, heavy rainfall and droughts, etc. (WHO 2015). Climate change
is drastic variations and shifts of weather conditions (moisture, cloudiness, precip-
itation) from warm and moist climate to cool climate due to external or in internal
factors over different time scales (Singh 2009).
The main cause of climate change in South Asia is the increase in concentration of
greenhouse gases (GHGs). The concentration of one of the major GHGs, carbon
dioxide (CO2), has been constantly increased in South Asia due to rapid industrial-
ization and other anthropogenic activities. India and Pakistan are the major
contributors of CO2 emissions in this region, while, in terms of per capita emissions,
Maldives is the highest contributor. This changing climate is manifested in the form
of global warming, changing rainfall patterns, melting of glaciers, sea level rise, and
increase in the frequency and intensity of cyclones or floods. Since 1950s, the
number of cold days and nights decreased, while number of warm days and nights
increased (IPCC 2014). The geophysical and demographic conditions make the
region more vulnerable to climate change. Impacts of climate change are visible
now in water resources, agriculture, forests, and ecosystems. It is affecting the well-
being of billions of people in the South Asian region.
Climatic Events
The most dangerous climatic event of South Asia is cyclone. Cyclones are most
destructive in low-lying coastal region especially in Bangladesh and India. High
waves slough large coastal parts and cause severe damages and kill thousands of
people. In 1970, a cyclone killed more than 300,000 lives in Bangladesh (BBS
2017). The frequency and intensity of droughts also increased in South Asia
(Webster et al. 1998; PAGASA 2001; Lal 2003). Consecutive droughts in 1999
and 2000 in Pakistan and India steered to a sharp decline in water tables and crop
failures. Longer duration of heat waves was observed in South Asia region, espe-
cially in India (De and Mukhopadhyay 1998). Moreover, the increased frequency of
intensive rainfall events along with some anthropogenic issues causes severe land-
slides, floods, and mudflows (Khan et al. 2000; Shrestha et al. 2000; Mirza 2002).
Globally, South Asian countries are most vulnerable in terms of floods (UNDP
2004). Since 1984–2017, Bangladesh has experienced seven severe floods and more
devastating was in 2007 that affected 10,655,145 people (BBS 2017). In 2005
Mumbai faced more hazardous floods that led to a loss of over 1000 lives, and a
total loss was more than US$250 million (IPCC 2007). In Pakistan, due to floods
almost 2000 people died in 2010 and leaving behind 20 million homeless people
with a loss of $10 billion. Only in Sri Lanka, from 2005 to 2014, the total number of
people affected by floods were 4,626,078. Bhutan was affected by three major floods
in 2009, 2011, and 2013. Landslide is another common event in South Asia. Bhutan
suffered by annual occurrence of landslides (NEC 2008), and in Bangladesh it killed
152 people only in 2017.
Geophysical Setting
The South Asia covers only 4.8% of the world’s land surface area but provides home
for above 24% of the world’s population and growing at an alarming rate of 1.8%
annually (Kakakhel 2012). This demographic coverage of South Asia gives a shelter
for 39.49% of total Asia’s population.
The South Asia is surrounded by three water bodies – the Bay of Bengal, the
Indian Ocean, and the Arabian Sea. Moreover, it has highly varied climate zones
from snowy highlands to sun-scorched deserts. The region is the quay of various
topographies, for example, glaciers, rainforests, mountains, plateaus, beaches, val-
leys, deserts, savanna, and grasslands.
Climatic condition of South Asia ranges from arctic temperatures that found in
the high mountains to a temperate in the foothills and on the Indo-Gangetic Plain to
tropical environments on the Deccan Plateau. Diversified geophysical settings with
varieties of climatic condition make the region more prone to different types of
environmental issues.
Glacier Melt and Sea Level Rise
There are three main seas in South Asia and are vulnerable to sea level rise. Sea level
rise is a gradual process and aggravated with global warming. The ice mass of the
Himalayas is melting rapidly than the global average rate and creates great threat to
this region. Sea level rise emerged in the Bay of Bengal in 1947, and the rising rate is
1.4 mm and 3.9 mm per year in the southeast and south-central part nearest to the sea
of Bangladesh (MoEF 2012). More than 100 million hectares of arable lands of
Bangladesh are affected due to sea level rise. It is predicted that sea level will rise
45 cm by 2050 and will affect 10–15% of the land area and near about 35 million
people. Sea level rise first appeared in Indian Ocean in 1960s (CDKN 2014) and may
rise up to 15–38 cm by 2050. Coast land of Sri Lanka is less than 1 m above sea
level. Average elevation of the Maldives’ is 1.5 m above sea level and its highest
point is less than 2 m. About 47% of all dwellings of the country are located at high
risk of sea level rise within 100 m of the coastline, and these are the home of 42% of
total population (Das 2010). The total islands are affected by saline water intrusion,
and a rising tide may submerge the islands easily. The major problems of sea level
rise are saline water intrusion, threatening drinking water supply, agricultural land
degradation, and aquaculture damage.
Land Degradation
Land degradation due to water and wind erosion is a common phenomenon in South
Asia. South Asia has nearly 90 million ha irrigated land that is seriously affected by
water erosion. Irrigated cropland of Bangladesh, India, and Pakistan is severely
affected by salinity-induced water erosion. Afghanistan, India, and Pakistan are suf-
fering by another type of erosion, wind erosion due to desertification (UNEP 1997a).
Water Scarcity
Many parts of South Asia are suffering from water scarcity. Parts of Afghanistan,
India, and Pakistan are distressed of water shortage due to desertification. Some
parts of India, Bangladesh, and Sri Lanka are facing the problem of lowering of
groundwater table. Maldives is facing depletion of freshwater due to salinity

intrusion. Moreover water pollution (UNEP 1997b) from industrial wastes, agri-
cultural runoff, commercial pesticide, and arsenic contamination decreases usable
water availability.
Ecosystems and Biodiversity Loss
Within South Asian countries, highest rate of deforestation is found in Pakistan.

Deforestation leads to habitat and species loss that tends to ecosystems and biodi-
versity depletion. Mangrove forests in Bangladesh, India, and Sri Lanka (UNEP
1997b) are also under pressure for shrimp cultivation and salt production.
Pollution
With increasing urbanization and demographic pressure, pollution is becoming a

vital concern in South Asia. Increased industrial activities, vehicles, and brick kilns
increase regional pollution over time, and GHG emission has risen in South Asia by
approximately 3.3% annually since 1990 (Khwaja et al. 2012). India is the highest
air-polluting country in this region followed by Pakistan (Khwaja and Khan 2005).
In Bangladesh air is polluted mainly by vehicular emissions, industrial emission, and
brick kilns. In Bhutan, forest fire is the main source for air pollution. In Nepal air
quality is deteriorating with high levels of dangerous pollutants (Khwaja et al. 2012).
In Sri Lanka key source of air pollution are motor vehicles, burning of domestic and
industrial wastages, firewood, etc. (Senarath 2003).
Import of Hazardous Wastes in South Asia
Disposal of industrial waste in environment increases the pollution level in land, air,
and water. The international waste traders always searched for welcoming dumping
grounds in third worlds as waste importer. And South Asia is more recent discovery
by them. Different types of waste such as plastic waste, metal waste, tin waste, iron
waste, lead waste, etc. are imported in South Asia consciously or unconsciously. For
example, in late 1991, four US corporations secretly mixed 1000 t of hazardous
waste containing high levels of lead and cadmium into a shipment of fertilizer which
was imported by Bangladesh, and one third of that toxic fertilizer was applied on
farms (Leonard 1993). In 1992, the South Asian countries imported only 15% of the
US plastic waste. But in 1993, Bangladesh, India, and Pakistan imported 53% of
total US plastic waste deliberately (Leonard 1993). These various nondegradable,
slow degradable chemical and hazardous wastes cause environmental degradation
and health hazards too. Banning the international waste trade may be a solution to
protect the importer countries. But, developing environmentally sustainable produc-
tion processes for every country will be the better solution.
Country Basis Environmental Issues, Causes, Vulnerable Areas,

and Overall Impacts
Afghanistan
Afghanistan is a landlocked country of South Asia with 652,000 km2 land area. It is a
mountainous and very arid country of South Asia. Agriculture is the primary source
of livelihood. Continuous drought and extensive degradation of its natural and
biophysical resources are stunting its future development and making it more
vulnerable to climate changes (Table 1).
Bhutan
Bhutan is also a landlocked country in South Asia. It is located at the eastern end of the
Himalayas. The country is bordered by China to the north and by India to the south,
east, and west. It contains most abundant forest and water resources. The country is
considered as a sanctuary for biodiversity and a model for environmental stability. But,
now a days, climate change creates many threats to Bhutan. This country is more
susceptible to flash floods and landslides due to accelerated glacier melt (Table 2).
India
In consideration of area, India is the largest country of South Asia and the seventh
largest country in the world. The vastness of the country provides diverse
Table 1 Environmental issues, causes, vulnerable areas, and overall impacts in Afghanistan
Key environmental
issues Main causes Vulnerable areas Impacts
Soil degradation; Population growth; Agriculture; water Water scarcity; high
deforestation; loss of increased demand for resources; temperature; reduced
biodiversity; agricultural lands, ecosystems; natural precipitation;
overgrazing; fuelwoods, housing calamities; human increased
desertification; soil materials, etc. health; and social evapotranspiration;
erosion; air pollution; development vulnerability of
water pollution; food agriculture, wetlands
security risks; natural and ecosystems to
disasters such as desertification; food
earthquakes and insecurity; duration
droughts and frequency of
drought; flash
flooding from glacial
melt; increasing risk
from malaria;
malnutrition and
migration
geographical settings and varied climatic regimes from humid to arid that makes the
land more vulnerable to the diverse environmental problems (Table 3).
Maldives
Maldives, situated in the Indian Ocean, is an island nation of South Asia which
consists of coral reefs and hundreds of smaller islands. It is the smallest South Asian
country both in population and area. The coral reefs are the seventh largest in the
world and rich in biodiversity and aesthetic value. The country is exposed to the risks
of extreme climatic events, sea level rise, and saline intrusion (Table 4).
Table 2 Environmental issues, causes, vulnerable areas, and overall impacts in Bhutan
Key environmental
Soil erosion; air Rapid Agriculture; ecosystems Agricultural yield
pollution; water urbanization and biodiversity; water reduction; forest area
pollution; scarcity of resources; human degradation;
drinking water; health; and natural biodiversity and habitat
deforestation; solid calamities loss; floods; vector-
waste disposal; climate borne and waterborne
change; and glacial melt diseases
Table 3 Environmental issues, causes, vulnerable areas, and overall impacts in India
Key environmental
Deforestation; soil Urbanization; Agriculture; water Sea level rise;
erosion and land industrial effluents; resources; coastal, increase of sea
degradation; emissions from terrestrial, and marine temperature; frequent
desertification; vehicles and brick ecosystems; human and intensive floods,
overgrazing; loss of kilns; unmanaged health; urban area cyclones and
biodiversity; air ecotourism; droughts; glacial
pollution; surface agrochemicals; melting; increased
water pollution; fossil fuel burning temperature; changes
arsenic contamination in precipitation
in groundwater; forest patterns; floods;
and agricultural land- saline intrusion; heat
use change; waves; water- and
demographic airborne diseases;
pressure; climate decreased agricultural
change; natural production;
disasters such as biodiversity loss; and
floods, cyclones and impacts on urban
landslides; sea level infrastructure,
rise; glacial melt; drainage, sanitation,
salinity intrusion etc.
Table 4 Environmental issues, causes, vulnerable areas, and overall impacts in Maldives
Key environmental
Climate change; sea Demographic Coral reefs; coastal Ecosystem damages,
level rise; saline water pressure; and marine loss of coral reefs;
intrusion; coastal marine-based ecosystems; water salinity intrusion in
erosion; groundwater tourism; sea resources; disasters groundwater; increased
depletion; marine level rise and hazards; tourism; intensity and frequency
biodiversity loss; air and public health; social of climatic hazards
water pollution; waste development such as cyclones,
generation; coral reef flooding, and
bleaching inundation of islands;
diseases; disturbance in
tourism; and migration
Table 5 Environmental issues, causes, vulnerable areas, and overall impacts in Nepal
Key environmental
Deforestation; soil Rapid urbanization; Agriculture; water Increased intensity of
erosion and emissions from motor resources; glacier lake outburst
degradation; water vehicles and terrestrial floods due to rapid
pollution; air industries; increased ecosystems and glacial melt;
pollution; loss of demands for timber; biodiversity; intensified scarcity of
biodiversity; waste population growth; human health water; outbreaks of
generation and lands conversion diseases; agricultural
disposal; climate production loss;
change; ice cap glacial melt dependent
melting; natural ecosystems and
disasters biodiversity loss
Nepal
Nepal is one of the three landlocked countries in South Asia. It is located at the foot
of world’s highest mountains the Himalayas and bordered by China to the north and
India to the south, east, and the west. Its topography ranges from very high altitudes
of the Himalayan Mountain to the Gangetic Plains. Agriculture is the main liveli-
hood option. This country is vulnerable to the climatic events too (Table 5).
Pakistan
Pakistan, the second largest country of South Asia, comprises dry or cold climatic
regimes. It is bordered by India to the east, Afghanistan to the west, Iran to the
southwest, and China in the far northeast. Alike climatic zones, geography also
varies across the country. Near 60% of the total watershed area of the Indus basin lies
within Pakistan’s territory. Main climatic changes found in these areas are glacial
melt, sea level rise, and drought (Table 6).
Table 6 Environmental issues, causes, vulnerable areas, and overall impacts in Pakistan
Key environmental
Water pollution; Urbanization; Agriculture; coastal Increased intensity
seasonal scarcity of industrialization; zones; marine and and frequency of
freshwater in natural wastes disposal; terrestrial drought; coastal
resources; soil population pressure; ecosystems; water erosion and salinity
erosion; coastal unplanned resources; land intrusion from sea
habitat loss; ecotourism; resources; climatic level rise; increased
degradation in marine mangroves depletion events; health and natural disasters;
ecosystems; natural for aquaculture; social development changes of sea and
disasters, overfishing; atmospheric
deforestation; increased demands temperatures; several
desertification; for timber and flooding and future
biodiversity loss; fuelwoods; hunting drying of water
climate change; air and poaching; resources due to
and water pollution excessive use of glacial melt; reduced
agrochemicals soil productivity and
fertility, reduced crop
production; food and
water insecurity;
land-use changes;
increased intensity of
drought and
desertification; longer
exposure to water
logging; outbreak of
heat-related and
vector-borne
diseases;
malnutrition;
migration; and
conflict
Sri Lanka
Sri Lanka is also an island country in South Asia and bordered by India and
Maldives. The country is rich with mountainous and coastal biodiversity. Weather
condition of the country is hot and humid. Part of the country experiences long-term
dry spells, and extensive areas suffer from water deficit. The country is in tremen-
dous risk by predicted changes in climatic condition in terms of temperature,
frequency and duration of drought, intensity of rainfall and storm surges, and sea
level rise (Table 7).
Bangladesh
Bangladesh, the largest delta on earth, is situated in South Asia. It is located between
20 340 and 26 380 north latitude and 88 010 and 92 410 east longitude (BBS 2017). It
Table 7 Environmental issues, causes, vulnerable areas, and overall impacts in Nepal
Key environmental
Deforestation; loss Human pressure; Agriculture; coastal Reduced crop
of biodiversity; increased demand for and marine production due to
coastal degradation; timber; unplanned ecosystems; water high temperature and
land degradation; marine-based resources; fisheries; sea level rise;
soil erosion; waste tourism; poaching; public health; natural damages to
generation; pollution sea level rise; disasters settlements,
by municipal and industrial and industries, and
domestic waste; municipal waste livelihoods in coastal
limited access to disposal areas; ecosystem
potable water; degradation and
waterborne diseases; biodiversity loss in
air and water coastal and marine
pollution; climate ecosystems; saline
change water intrusion into
the freshwater and
groundwater;
increased incidence of
vector-borne
diseases; imbalanced
climatic events;
threats to ocean;
threats to food
security, fishery, and
livelihoods; and coral
reef bleaching
is bordered by India on the west, north, and east, by Myanmar on the southeast, and
by the Bay of Bengal on the south (Fig. 1). The area of the country is 147,570 km2.
Most of the country is low-lying comprising mainly the delta of the Ganges and
Brahmaputra rivers. A total of 80% of the country is floodplain (Agrawala et al.
2003). Mean elevations range from less than 1 m on tidal floodplains, 1–3 m on the
main river and estuarine floodplains, and up to 6 m in the Sylhet basin in the
northeast (Rashid 1991). Only in the extreme northwest, elevations are greater
than 30 m above the mean sea level. The northeast and southeast portions of the
country are hilly, with some tertiary hills over 1000 m above mean sea level (Huq
and Asaduzzaman 1999).
The climatic condition of Bangladesh is tropical monsoon. It has a hot and rainy
summer and a dry winter. January is the coolest month with an average temperature of
26 C, and April is the warmest with temperatures ranging from 27 C (east) to 40 C
(west). The climate is one of the wettest in the world. In the rainy season, most places
receive above 1525 mm rainfall annually, and hilly areas receive about 5080 mm.
Maximum rainfalls occur from June to September all through the monsoon and least
from November to February during the winter season (Banglapedia 2014).
The environment of the country is under severe pressure due to changing climate
and destructive anthropogenic activities. Environmental degradation is directly and
Fig. 1 Map of Bangladesh
indirectly affecting human health, ecosystems, and economic growth of the country.
Demographic pressure, poverty, lack of proper awareness on environmental issues,
and lack of implementation and monitoring of environmental rules are the main
causes for existing environmental condition of Bangladesh (GEDPCB 2015).
As environment is a vast area and each part is linked with others. Changes in any
part or issue are responsible for changing the other parts. The major environmental
issues and problems in Bangladesh are climate change, natural calamities (lightning,
cyclone, flood, flash flood, drought, earthquake, riverbank erosion, sedimentation),
geospatial setting, environmental pollutions (air pollution, water pollution, soil
pollution, and noise pollution), ecosystem changes, deforestation, forest fire,
desertification, salinity intrusion, waste disposal, salt/shrimp cultivation, brickfield,

exotic species, etc.
Climate Change
Among all countries of South Asia, Bangladesh is the most vulnerable one to climate
change (Huq 2001; Rahman and Alam 2003; UNDP 2007) because of its unfavor-
able geographic location, flat- and low-lying topography, high population density,
high levels of poverty, livelihoods reliance on climate-sensitive sectors like agricul-
ture and fisheries, and inefficient institutional aspects (Climate Change Cell 2006).
Change of climatic condition affects adversely in every sectors directly or indirectly.
But the most disparaging effects of climate change are sea level rise, higher
temperatures, unexpected monsoon precipitation, increased flooding both in terms
of extend and frequency, frequent cyclonic hazards, drought, salinity intrusion, and
increasing temperature (Huq and Ayers 2008). Impacts of climate change are
extremely detrimental to the national economy, environment, and national develop-
ment (Reid and Sims 2007).
Human health is severely affected by weather and climate. Climate change
induces health problems, such as cardiovascular and respiratory diseases, infectious
diseases, malnutrition, and even deaths. On the other side, it is declining water and
food securities and undermining infrastructures, health systems, and social protec-
tion systems (WHO 2015).
Global Warming
The world’s temperature is increasing day by day, and it is predicted by the
specialists that due to climate change the global temperature will rise between
1.80 C and 4.0 C by the year 2100, although it could possibly be 6.4 C (Alley
et al. 2007). In case of direct effects of temperature, Bangladesh experiences the
most rapid rates of warming, degradation of land, diseases in human, and demolition
in local livelihoods and biodiversity. As well as, in case of indirect effects, hotter
weather increases the number of deaths and illness due to heat, particularly in older
people and urban poor (Depledge and Lamb 2005).
A research was conducted in Bangladesh from 1983 to 2009 and found a
relationship between mortality rate and temperature (Alam et al. 2012). From 1961
to 1990, the rate of heat-related deaths in elderly persons (65+ years) was 4 deaths
per 100,000 annually. It is increasing rapidly after 1990, and the devastating death
occurs during the 8-day heat wave in 2008 (WHO 2015). During those 8 days, more
than 3800 people died from the excess heat. Two thirds of those were 65 or older
which indicates that the elderly are especially more vulnerable to heat waves
(Gawthrop 2017). In 1990 the warm spell was 60 days. But a projection by WHO
(2015) revealed that under this environmental condition, the warm spell will be
almost 300 days by 2100, and death rate will increase at 30 per 100,000 people by
2080. Only a systematic reduction of global warming could limit warm spell days to
120 on average and heat-related mortality at 7 per 100,000 people.
The increasing temperature directly effects on food production sector. Crop yields
directly depend on climatic conditions (temperature, rainfall, etc.), and higher
temperature leads to large declines in cereal production (Stern 2006). A long-term

increase of temperature in water will increase the concentration CO2 that make the
harbor of fishes more acidic. Some fishes and aquatic fauna are intolerable to acidic
water and may become extinct with time (Pender 2008).
Geophysical Setting
Bangladesh covers a land area of 130,170 km2 containing 162 million people, and
the population density is 1251.8 people per km2. Bangladesh covers diverse geo-
physical features – floodplains (80%), terraces (8%), and hills (12%) (BBS 2017).
Moreover, the evergreen, deciduous, and mangrove forest depicts diversified phys-
iography (Ahmed and Vijnan 1997). Furthermore the seasonal monsoon climate of
the country is rich with high rainfall, high humidity, and high and low temperatures
(BBS 2016). These varied geophysical settings expose the country to rapid environ-
mental changes and natural hazards.
Demographic Pressure
Bangladesh is one of the most densely populated country in the world (Huq et al.
1998). Population pressure is an obstacle for Bangladesh to achieve major two broad
goals – socio-economic development and reduction of poverty. Population density of
Bangladesh was 196 per km2 in 1901 (Huq et al. 1998) increased to 1251.8 per km2
in 2016. Now the average annual growing rate is 2.08%, and if the population
increases in such a rate, then the “carrying capacity level” of the country will be
collapsed.
Population pressure is the main culprit for environmental changes (Bremner et al.
2010) and also the vital factor for rapid land-use and cover change (Vanclay 1993;
Wibowo and Byron 1999) and deforestation deforestation (Amelung and Diehl
1992; Mather and Needle 2000). Rising of population leads to excessive demands
for housing and consumption of goods and services. For meeting the additional need
of house and foods, existing agricultural lands are converted into building construc-
tion, and marginal lands like forest lands are brought under cultivation (Fig. 2).
Encroaching and deforestation causes soil erosion, loss of soil fertility, siltation,
flooding in river basins, changes in microclimate, habitat loss, loss of genetic
diversity, ecosystem loss, and damages of environmental balance. Moreover,
low-lying areas are also invaded for more housing and cultivation of more food
grains; thus habitats of fish are encroached. Similarly, shrinkage of pasture land
affects livestock resources. Thus growing people over exploit the natural resources
of the country (Huq et al. 1998) and induce ecological hazards.
Unplanned Urbanization and Industrialization

Urbanization is closely linked with industrialization (Rahman 2012). Moreover,
urbanization, migration, and development are also interlinked (Kawsar 2012). But,
in Bangladesh rapid urbanization is the greatest challenge of twenty-first century
because of unplanned and uncontrolled urban growth (Khan 2016). Total land of
urban area covers 10,600 km2 which is only 7% of the total land but contains 34% of
the total population (LGED 2017).
Fig. 2 Forest lands are converted into agricultural land
The country was predominantly agrarian and rural. In 1951 only 4% of the
population lived in urban area. Urban population increased moderately to about
8% by 1971. But it grew rapidly after independence at 19% by 1991. Saha (1989)
reported that increased industrialization in Bangladesh increases urbanization in that
period. In 2005, about 26% of the total population was found in urban area while
28% by 2011 and 34% by the end of 2016. If this growth rates exist, then the
country’s urban population will reach at 79 million or 42% of the total population by
2035 (LGED 2017).
Growing urbanization creates numerous problems and challenges for the growing
people including poor housing and transport; inadequate drinking water; lack of
drainage and sewerage; high percent of people living in slums; inadequate urban
basic services especially water, electricity, sanitation, and gas; dumping of huge
wastages on open land and in rivers; increasing industrial pollutions; social and
political conflict over land resources; and high level of vulnerability to natural
disasters (LGED 2017). Unplanned urbanization not only depletes the country’s
natural resources but also degrades the environment.
Unplanned Construction of Brick fields

Brick burning contributes to climate changes and global warming by absorption of
greenhouse gases in the atmosphere in higher quantities (IUSS 2002). Brick kilns
produce long-term and short-term impacts on the environment. Deforestation,
reducing agricultural yields, damaging arable lands, air pollution, etc. are the short-
term effects, while climate change, global warming, impacts on human health, ozone
layer depletion, etc. are the long-term effects (Pokhrel and Lee 2011). Collection of
soil from agricultural land, mountains, and hillocks for manufacturing bricks
(GEDPCB 2015) removes topsoil, and it takes 25–30 years for those lands to regain
fertility. Brickfields near the rivers or other water resources cause great impacts on
fish production, aquatic plant survival, and aquatic ecosystems (Jerin et al. 2017).
In Bangladesh there are approximately 10,000 brick kilns (Fig. 3). According to the
Bangladesh Brick Manufacturing Association, for growing Dhaka City, it needs to
manufacture 3.5–4 billion bricks per year. According to the estimation of Department
of Environment, about 430 metric tons of fuelwood are required for manufacturing one
million bricks. Fuelwoods used in brick kilns are approximately 25% of total fuel used
in Bangladesh annually (Islam 2001). Bangladesh Forest Research Institute (BFRI)
estimated that, on average, 8000 ha of reserve forests are deforested annually where
brick manufacturing plants play a vital role in this destruction. Moreover, the chimneys
used by the manufacturers are totally environment unfriendly and spread unsafely the
poisonous vapors, dust, carbon dioxide, carbon monoxide, sulfur dioxide, florin, and
lead into the lower atmosphere. Brick kilns are the main source of fine particulate
pollution in Bangladesh and produce nearly 40% of total emissions. The Bangladesh
Country Environmental Analysis reports that emissions of particulate matters from this
kiln cluster are responsible for 750 premature deaths annually (Sarker 2012). In
Fig. 3 Unplanned brick field construction on the bank of Buriganga River

general different types of diseases like skin disease, eye irritation, and respiratory
problems are recorded around the brick manufacturing kilns.
Sea Level Rise and Salinity Intrusion

Vast coastal area, high population density, and high poverty rate and reliance on
natural resources tend Bangladesh to be one of the most vulnerable countries to
extreme weather events. Almost 25% of the total population live in coastal areas and
under threat of storms, sea level rise, and tropical cyclones. At present, saline
intrusion into the agricultural lands, drinking water (Fig. 4), and livelihoods reaches
at 100 km upland from the Bay of Bengal (Khan et al. 2011). Sea level rise is a long-
term process, and if continued, an annual average of 7.2 million people will be
affected between 2070 and 2100. If there is proper protection like construction
and raising of dikes, the effect could be limited to about 14,100 people only
(WHO 2015).
If the sea level rise up to 1 m, Bangladesh could lose 15% of its land area and
around 30 million people could become refugees. It will effect on agriculture,
industry, infrastructure, livelihoods, marine resources, forestry, biodiversity, fisher-
ies, human health, and other utility services by flooding and salinity intrusion
(Denissen 2012). IPCC predicted that due to sea level rise, 17% land area, 30%
food production, and 20 million people will directly be suffering by 2050.
Fig. 4 Indigenous water collection technique at high saline period

Natural Calamities in Bangladesh

Currently Bangladesh is ranked worldly as one of the most disaster-prone countries.
Almost 97% of the total land area are at risk of multiple hazards including tropical
cyclones, floods, droughts, and riverbank and coastal erosion (Alam 2016). The
natural disasters that Bangladesh experiences frequently are described in the follow-
ing paragraphs.
Flood and Flash Flood

Among all disasters, flood is more hazardous in Bangladesh. Floods in Bangladesh
are more frequent and cause a pronounced national economic damage. Bangladesh is
a low-lying country with 54 trans-boundary rivers (Alam and Siddiqi 2007) that
carry huge floodwater during the monsoon. Almost 80% of the total area of the
country is prone to flooding. Catastrophic floods occurred on average of every
10–20 years – 1974, 1987, 1988, 1998, and 2004. Direct impacts occurred on
agriculture, fisheries, drainage, infrastructures, industry, trade, commerce, utility
services, as well as urban and rural lives (Denissen 2012).
Flash floods occur mostly in the northeast and southeast regions of Bangladesh
caused by heavy rainfall in bordering hilly regions (Fig. 5). During flash floods the
violent inflow from the hills run offs and washes away infrastructures, crops, and
lives. Because of the steeper gradients in hilly areas, flash floods have less travel time
and short-lived but more violent, sometimes causes landslides. Flash floods
Fig. 5 Flash flood overflows the stream in the Chittagong Hill Tracts (CHTs)
sometimes also occur in the northwestern region of Bangladesh due to heavy,

localized rainfall (Alam and Siddiqi 2007).
Cyclone
Bangladesh experiences significantly frequent tropical cyclones each year (Salek
1998; Paul 2009; Haque et al. 2012). At present 8.3 million people are living in
cyclone-prone area, and Tanner et al. (2007) anticipated that it will be nearly 20.3
million by 2050. South and south-eastern parts of the country are more exposed to
and hit by tropical cyclones during last few years (Figs. 6 and 7). In Bangladesh,
women are especially vulnerable to cyclone. During the most devastating cyclone in
1991, the death rate in case of women was almost five times higher than the men
(Denissen 2012).
Riverbank Erosion
In Bangladesh per capita cultivated land is only 12.5 decimals, and around 52% of
rural population are functionally landless. Moreover, every year roughly 1% of farm
land is being converted to nonagricultural uses (Quasem 2011). In such condition,
any loss of land by riverbank erosion is shocking (Rana and Nessa 2017). Rivers are
dynamic in nature and riverbank erosion is a natural process (Fig. 8). Channel
changes due to bank erosion in one side and accretion of land in another side are
the natural process. But sometimes it occurred due to anthropogenic activities like
sand mining, infrastructure building on the riverbank, artificial cutoffs, construction
Fig. 6 A single patch of Sidr (disastrous cyclone of 2007) affected Sundarbans after 4 years of
attack
Fig. 7 Damages by Sidr in the core zone of the Sundarbans
of reservoirs, land-use alterations, etc. (Li et al. 2007; Uddin et al. 2011). River bank
erosion causes socio-economic losses rather than killing. Loss of houses and agri-
cultural land forces people for migration. Due to riverbank erosion in Bangladesh,
almost 129,853 people were displaced yearly (Mollah and Ferdaush 2015).
Lightning
Lightning is an emerging environmental issue throughout the world including
Bangladesh. About 24,000 deaths and 240,000 injuries occur globally per year due
to lightning (Holle 2008). Lightning injury is globally considered as leading cause of
weather-related death after tornadoes, flash floods, and hurricanes (Biswas et al.
2016). Bangladesh government also added lightning strikes to the country’s disasters
list (Islam 2016). Bangladesh is more prone to this type of disaster. Most lightning
deaths usually occur during the warm months of March to July and severe in month
of May (Tasin and Roy 2016).
According to the report of Dewan et al. (2017), since 1990 to mid-2016, a total of
5468 casualties occurred in Bangladesh comprised of 3086 fatalities and 2382
injuries. Previously, the fatality and injury rate were 0.92 and 0.71 (correspondingly)
per million people per year and become double in 2010 (1.6 and 1.4 per million
people per year, respectively). According to the Bangladesh Meteorological Depart-
ment, 1476 people have died from lightning in Bangladesh since 2010. The rural
portions are 93% more vulnerable than urban and male are more susceptible than
women. The more lightning-prone areas in Bangladesh are field (43%), house (22%)
(Holle 2009), water body (14%), and road (12%). Frequency and intensity of
Fig. 8 River bank erosion in the countryside of Bangladesh
lightning is linked with climate change, as climate change causes global warming,
leads to more evaporation, and causes more clouds that are more potential for
lightning storms.
Drought, Desertification, and Water Scarcity

Drought and desertification are other alarming environmental issues and greatest
challenges for Bangladesh (Ali 2007). North and northwestern regions of the country
are suffering from drought (Pender 2008) because of extreme temperature (Denissen
2012) and water deficiency (Stern 2008) (Fig. 9). Deforestation leads to desertifica-
tion in Bangladesh by reducing groundwater level that leads to soil dry, fragile, and
easily erodible. Desertification already started at the central Barind area in the
northwest part of the country. Besides deforestation, low soil fertility also causes
aridity that leads to land degradation and ultimately desertification. About 6.0
million ha (43% of total area) of Bangladesh was affected by various forms and
degrees of degradation (Ali 2007; Islam et al. 2010).
Desertification originated great economic losses and human sufferings than any
other environmental issues in Bangladesh. Since 1960–1991 drought occurred in
Bangladesh 19 times and affected about 47% area and 53% population of the country
(Fig. 10). Between 1969–1970 and 1983–1984, the relative effects of drought were
more damaging than flood on rice production (Ali 2007; Islam et al. 2010). Drought
and desertification affect directly on food production, biodiversity, water resources,
fisheries, socio-culture, economy, and human health. Moreover, mortality rate of
infant is twice in dry zones than the non-dry zones.
Fig. 9 Drying up of stream causes water scarcity
Pollution
Environmental pollution has become a major global concern in recent years as well
as in Bangladesh. Bangladesh is now facing a serious problem of air pollution,
water pollution, soil pollution, and noise pollution. Each and every of these types
of pollution has detrimental effects on environment, human health, biodiversity,
and quality of life. Major cities of Bangladesh – Dhaka, Chittagong, Khulna,
Sylhet, Rajshahi, Barisal, Gazipur, and Narayanganj – are more prone to the
pollutions.
Air pollution: Air pollution is one kind of anthropogenic generous environ-
mental pollution. It is associated with around 7 million premature death and
45 million new cases of chronic bronchitis globally each year (UNEP 2001). In
Bangladesh, air pollution has recently been receiving priority among all environ-
mental issues. According to World Health Organization (WHO) latest report,
Bangladesh has ranked fourth among 91 countries with worst urban air quality.
There are two main sources for air pollution in Bangladesh – industries and
vehicles. Industries and vehicles specially two-stroke engines produce enormous
quantities of harmful gases that pollute air (Shams 2017). Another major source
of air pollution is brick field that burn fossil fuels and produce a large portion of
air pollution.
Fig. 10 Drinking water collection during drought period
Indoor pollution by burning of biomass for cooking causes great threats to women
and children health. In Bangladesh, household air pollution is responsible for 61% of
total child deaths due to acute lower respiratory infections (Hales et al. 2014).
Particulate pollutants with the sizes of 10 μm diameter (Pandve 2008) or smaller
are more detrimental than gaseous pollutants. Particles can penetrate and lodge deep
inside the lungs and may cause cardiovascular and respiratory diseases and even
cancer in the lung or urinary tract or bladder in human body. It is assumed that
around 20–80% decrease in air pollution level in Bangladesh could save approxi-
mately 1200–3500 lives annually (GEDPCB 2015).
Water pollution: Water pollution is the second most devastating pollution in
Bangladesh. The main sources of water in Bangladesh are rainwater, surface
water, and groundwater (Ahmed 2015). Rainwater pollution includes acid rain that
directly linked with air pollution. The intensity of acid rain is low in Bangladesh,
sometimes found in Dhaka City. Surface water generally polluted by industrial
wastes (Islam et al. 2015), solid wastes, and sewage disposal. Mostly contributing
industries for water pollution are pulp and paper, pharmaceuticals, metal processing,
food industry, fertilizer, pesticides, dyeing and painting, textile, tannery, etc. Out of
230 main rivers of Bangladesh, more than 200 rivers directly or indirectly receive a
large quantity of untreated industrial wastes and effluents (Islam 2011). Everyday
approximately 700 tanneries of Dhaka city are discharging about 16,000 m3 of toxic
wastes (Alam 2009). About 4000–4500 t of solid wastes are generated daily
(Rahman et al. 1999), and most of that are discharging in low-lying areas or into
river water (Figs. 11 and 12). This contamination transports to human bodies through
food chain (Chakraborty et al. 2013).
Fig. 11 Water pollution in Buriganga River due to dumping of solid wastages
About 97% people of Bangladesh are using groundwater as the main source of
drinking water that has been threatened by arsenic contamination (Smith et al. 1998).
Seventy-five million people are at risk, and 24 million are potentially exposed to
arsenic contamination (Safiuddin and Karim 2001). Arsenic contamination of
groundwater in Bangladesh is considered the world’s largest case of water pollution
(Safiuddin and Karim 2001; Ahmed 2015). Groundwater is also polluted by infil-
tration of industrial wastes disposed on the ground or in surface water bodies,
intrusion of saline water, and extensive use of agrochemicals. Leaking sewers/septic
tanks/pit latrines also causes groundwater pollution.
Soil pollution: Soil is the main part of terrestrial ecosystems (Shahabuddin et al.
2010). After water, soil is the second most useful natural substance in Bangladesh
(Latif et al. 2008). This part is contaminated by pollutants arising from domestic,
municipal, industrial, mining, agricultural wastes, and agrochemicals (Kalantari
et al. 2006; Osman 2014). These hazardous elements increase the optimum level
of soil chemical substances and thus induce soil pollution (Kabata-Pendias and
Pendias 2001).
Most common chemicals such as petroleum hydrocarbons, heavy metals (chro-
mium, lead, copper, arsenic, etc.), pesticides, and solvents (Davis and Cornwell
1998) pollute ground soil generally in 4 ways – (1) discharging of industrial wastes,
(2) seepage from landfills and sewages, (3) close contact with contaminated water,
and (4) excessive and nonregulated use of agrochemicals. Underground soil is
Fig. 12 Water pollution in the city areas due to careless throwing of wastages in the drainage
systems
contaminated by leaching, infiltration, and percolation of pollutants (Kanta et al.

2014) along with above mentioned four ways.
Industrial wastes deteriorate soil-water-plant system (Islam et al. 2006; Shamsad
et al. 2009), produce pollutant gases, increase soil salinity, and mix with food chain.
Soil pollution causes ecosystem loss and ecological imbalance; decreases soil
fertility, crop yield, and soil nutrient; and increases soil erosion, water logging and
inundation, pollutant in water, and public health problems.
Noise pollution: According to the World Health Organization (WHO), noise is
considered as the third hazardous environmental pollutant in Bangladesh following
air and water pollution (Muhit and Chowdhury 2013). Noise pollution produces
from traffic, airports, ports, railroads, industries, construction works, loudspeakers,
and in broader sense from urbanization (Dewan et al. 2012). Effects of noise
pollution include hearing loss in human, nervous disorder, hypertension, headache,
indigestion, peptic ulcer, degradation in lifestyle even death, and wildlife
disturbances (Kadiyali 1997; Tanvir and Rahman 2011). Ahmed (1998) reported
about 5–7% patients of Bangabandhu Sheikh Mujibur Rahman Medical University
(BSMMU), Dhaka, admitted themselves due to permanent deafness from noise
pollution (OECD 1995). Noise pollution also creates birth defects and changes in
immune system (Passchier-Vermeer and Passchier 2000). It also increases workplace
accident rates, stimulating aggression, and antisocial behavior (Kryter 1994).
According to World Health Organization (WHO), 60 decibel (dB) sound can make a
man deaf temporarily, and 100 dB sound can cause complete deafness. According to
the Department of Environment (DOE), in peaceful areas the perfect sound condition
for Bangladesh is 45 dB for the daytime and 35 dB for the night, while in case of
residential areas, 50 dB sound is considerable for the daytime and 40 dB for night. At
present noise level in Dhaka City of Bangladesh is measured between 60 and
100 decibel (Alam 2009). Daily variation of noise level in decibel at different
locations of Dhaka City is represented in Table 8.
If this condition continues, then 50% people of Dhaka City will lose 30 decibel of
hearing power by the year 2017 (Alam 2009).
Ecosystem Changes and Biodiversity Depletion

Bangladesh is a tropical country (Khan et al. 2007) and harbor of rich biological
diversity (Hossain 2001). It was assessed that altogether about 5700 species of
angiosperms (excluding gymnosperms) and 1500 species of fauna have been avail-
able in the country (Hossain 2001), but recently the population of some of the
species have declined to about a half.
Bangladesh has got a wide diversity of ecosystems. The vast ecosystem was
found in the world’s largest mangrove forests in Bangladesh. It has an area of about
601,700 ha and covers 4.13% of the country and 38.12% of the state forest land. A
total of 334 species of trees, shrubs, and epiphytes and 269 species of wild animals
have been identified here. The most significant is the famous Royal Bengal Tiger.
But the ecosystem is changing and biodiversity is declining day by day due to
climate change impacts and human activities, and the Sundarbans are likely to suffer
the most.
Growing people depend on forests and aquatic ecosystems for livelihoods and
pose a serious threat to biodiversity and ecosystems through illegal cutting,
encroachment, poaching, and land grabbing (Kibria and Haroon 2017). Since 1880
to till now, 14 animal species have been extinct in Bangladesh (BFD 2017).
According to IUCN Bangladesh Red Data Book (2000), there are 266 species of
inland fishes, 442 marine fishes, 22 amphibians, 109 inland reptiles, 17 marine
Table 8 Noise pollution in decibel at different places in Dhaka City

Location
Science
Time Gulshan Gulshan lab Saydabad Farmgate Dhanmondi Uttara
interval Commercial Residential Mixed Commercial Commercial Residential Residential
7–11 am 80.08 76.16 76.24 83.27 80.07 75.87 76.25
11 am–3 79.34 74.83 75.19 83.89 78.86 74.38 74.81
pm
3–7 pm 81.13 76.11 77.23 84.37 81.96 75.21 76.81
7 pm–1 78.52 74.31 75.32 82.08 80.28 76.30 73.36
am
Source: Alam (2009)
reptiles, 388 resident birds, 240 migratory birds, 110 inland mammals, as well as
3 species of marine mammals in Bangladesh; out of which 54 species of inland
fishes, 8 amphibians, 58 reptiles, 41 resident birds, and 40 mammals are threatened
throughout the country. Among the marine and migratory species of animals, four
fishes, five reptiles, six birds, and three mammals are threatened. When an ecosystem
losses a species, then total ecosystem and environmental balance collapsed.
Introduction of Exotic Species

Biological invasion has become a burning environmental issue globally as it dom-
inant over native ecosystems (Seabloom et al. 2006) and changes climate over time
(D’Antonio and Vitousek 1992). To meet the basic needs of growing population,
alien species were introduced deliberately in Bangladesh. Some flora was introduced
due to their economic value (Tectona grandis) and rapid growth (Acacia
auriculiformis). Mono-crop plantation of Tectona grandis initiated at Kaptai,
Chittagong in 1871 by clear felling the natural forests creates a great environmental
hazard. Teak plantation lacks undergrowth and is more subject to intense surface soil
erosion (Miah et al. 2014). Similarly, to meet food nutrition value, some fauna were
introduced too. A few of introduced flora and fauna became invasive later and cause
great threats to the environment.
The first widely introduced alien species in Bangladesh is water hyacinth
(Eichhornia crassipes) (Fig. 13) brought from Brazil during the British period for
Fig. 13 Invasion by water hyacinth in Kopotakkho River

its ornamental value. With time it became invasive in nature and vigorously spreads
throughout all wetlands (Pallewatta et al. 2003). Introduction of acacia and eucalyp-
tus into Bangladesh from Australia during the 1980s created great controversial
problems. These two genera are proven to be adversaries to the endemic flora and
found as environmentally unfriendly species to Bangladesh (Ameen 1999). More-
over out of all fish species that brought from abroad, 15 became more invasive. The
most disastrous ones are Clarias gariepinus (African magur), Pangasius giganticus
(giant pangas), and Oreochromis niloticus (nilotica). These were introduced from
Thailand between 1953 and 1990 (Rahman 1997).
Deforestation
Deforestation induces climate change and global warming and thus initiates other
environmental issues. Though forest area of Bangladesh is 17.62% of total land,
actual canopy coverage is only 6% (Fig. 14). Only deforestation is the culprit for this
forest condition. About 50% forests of the country have been destroyed by defores-
tation during last 20 years (Hossain et al. 2014; Rasel 2014; Chakma 2015).
Indiscriminate felling of trees for industrial purposes in the greater parts of Dhaka,
Mymensingh, and Rajshahi and for shifting cultivation in Chittagong Hill Tracts
resulted an alarming depletion of natural forests.
Population explosion is the prominent cause for deforestation faced by
Bangladesh. Country’s forests have been depleted since the early twentieth century
Fig. 14 Barren hills in Teknaf due to deforestation

due to increasing demand of land for agriculture, homes, and industries for over
population. In the 1980s, deforestation rate was 8000 ha per year, and now with
growing population, it is 37,700 ha per year. Deforestation causes soil erosion,
reduced rainfall, ecosystems and biodiversity damage, and species extinction and
prompts climate change.
Forest Fire
Large and irregular forest fires create intensive environmental impacts (Holmes et al.
2007). Forests of Bangladesh are tropical moist deciduous, so natural forest fire is a
sporadic event here. But intentional man-made forest fire occurred several times in
Bangladesh (Fig. 15) basically in the Sundarbans. In last 14 years, there have been
19 fire incidents occurred in the Sundarbans. This intentional fire usually is created
just before the monsoon in order to clear the lower land of forest to collect rainy
water for fishing.
Shrimp Cultivation and Salt Production

An enormous expansion of commercial shrimp cultivation and salt production
recently appeared as another major environmental issues. Shrimp cultivation
and salt production in the existing agricultural land (Fig. 16) or by encroaching
forest lands near the coastal zone affects soil and ecosystems terrifically since it
needs holding saline water for a long period of the year. Dikes of the shrimp
Fig. 15 Intentional forest fire in hill of Chittagong Hill Tracts

Fig. 16 Salt cultivation in agricultural lands of Teknaf
enclosures hinder the free flow of tide water which causes acute salinity mostly
during the month of April and reduce soil fertility rapidly. As a consequence,
the land becomes unproductive for further crop production. The severe con-
centration of salinity in the soil increases vegetation mortality rate and damages
forests.
Chakaria Sundarbans in Cox’s Bazar, Bangladesh, is an evidence of how
unplanned shrimp culture can destruct a natural forest rapidly. Historical records
of deforestation for shrimp cultivation represent that in 1972, the Chakaria
Sundarbans occupied an area of 19,000 ha. By 1981, this forest area shrink to near
9000 ha. In 1985, it was further reduced to only 4000 ha and again squeezed to half
by 1991 (Rasel 2014).
Sedimentation or Siltation
World’s largest delta, in Bangladesh, was affected by regular flood, riverbank
erosion, and sedimentation (Grosjean et al. 1995). The Ganges-Brahmaputra-
Meghna (GBM) delta is one of the most dynamic tide-dominated deltas in the
world (Haque and Rahman 2016). The GBM system carries the world’s highest
annual sediment load at one billion tons (Milliman and Syvitski 1992) (Fig. 17).
Seasonal overbank flooding during monsoon discharges 95% of total sediments
(Goodbred 2003) and has created a 16 km thick fluvio-deltaic sediment layer in
the Bengal Basin since the Paleogene (Allison 1998).
Fig. 17 Exposure of GBM delta to sedimentation (Source: http://www.goesr.gov)
All rivers of Bangladesh carry and deposit 2 billion tons of sediments per year in
the delta (ISPAN 1993; Rana 1993). The major effects of sedimentation are rising up
river basins and sea levels. Many rivers already lose their depth and disappeared
permanently due to sedimentation. Sea level of Bangladesh was 120 m lower 18,000
BP (Grosjean et al. 1995), and it is predicted that global sea levels could rise more
than 3 ft by 2100 (IPCC 2014). If the lower level of sea and rivers lifted up, then
flood intensity and salinity intrusion will increase more.
Excessive and Nonregulated Use of Agrochemicals

Bangladesh is mainly an agrarian-based country. To meet the demand for growing
population, farmers had to adopt a lot of strategies in different times. The most
adverse ones were use of chemical fertilizers, insecticides, herbicides, and pes-
ticides. Maximum farmers and dealers are illiterate and untrained. They apply
agrochemicals massively for getting rapid and huge amount of crops from their
small amount of land (Chakrabarty et al. 2014). Without examining the soil type,
excessive and indiscriminate use of agrochemicals may augment natural permis-
sible level of some radioactive elements in soil. Without direct attachment, this
kind of radioactivity could contaminate human body and other animals
(Rajendran 2003) by entering food chain and creates slow poisoning. Moreover
it causes a great threat to the soil and water ecosystems. Irrational use of
agrochemicals impacts on human health, environment, surface water, groundwa-
ter, soil and soil fertility, air, non targeted vegetation, and organisms (Aktar et al.
2009).
In Bangladesh, use of agrochemicals started in 1960 but it became more severe

since 1980. It is well established that insecticides cause acute and chronic toxicity on
human beings. According to the World Health Organization, pesticide poisoning
kills 25 million people globally every year (Mohammad 2012). Contaminated and
excessive use of agrochemicals expedites different types of diseases in Bangladesh.
Heart disease, kidney complicacy, hypertension, eye irritation, acidity, diabetes, liver
cancer, etc. are the most common ones.
Conclusion and Recommendations
Urbanization, industrialization, and burning of fossil fuel along with many other
factors are responsible for raising the CO2 level in the atmosphere and producing
other greenhouse gases in many ways (Khwaja et al. 2012). Raised CO2 and other
greenhouse gases are the major contributor to the global climate change and resultant
effects (IUSS 2002). To combat with climate change, site appropriate mitigation and
adaptation measure can be taken. For reducing greenhouse gases emission to safer
level, renewable energy sources like solar energy can be used in industries, vehicles,
brickkilns, and for cooking. Non-degraded forests and nonpolluted soil and water
can consume huge amount of CO2 from the atmosphere. Human pressure is the
rooted problem for rapid urbanization and industrialization, increased number of
vehicles and fossil fuel burning, pressurized land-use changes, and rapid climatic
changes with its adverse impacts (Bremner et al. 2010; Vanclay 1993; Wibowo and
Byron 1999). Developing the existing population into human capital along with
measures for controlling the future population size to desired level by reducing
growth rate could be proper solutions for mitigating all adverse environmental
issues.
Cross-References
▶ Air Pollution
▶ Air Pollution Prevention Technologies
▶ An Introduction to Sustainable Materials Management
▶ Environmental Impact of Steel Industry
▶ Homeopathic Nanomedicines and Their Effect on the Environment
▶ Impact of Climate Change and Land Use Change Scenarios on Water Resources in
Tha Chin River Basin: A Case Study of Suphan Buri Province, Thailand
▶ Indoor Air Pollution Around Industrial Areas and Its Effect: A Case Study in
Delhi City
▶ Industrial Solid Waste Management in a Developing Country Governorate and the
Opportunities for the Application of Cleaner Production Principles
▶ Integrated Assessment of Environmental Factors: Risks to Human Health
▶ Modern Air Pollution Prevention Strategies in the Urban Environment: A Case

Study of Delhi City
▶ Modern Environmental Materials, Pollution Prevention, Sustainability, and Green
World
▶ Soil Pollution and Remediation
▶ Status of Particulate Matter Pollution in India: A Review
▶ Wastewater Management to Environmental Materials Management
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Air Pollution
6
Saliha Saadet Kalender and Güler Bilen Alkan
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Types of Air Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Sources of Air Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
Effects of Air Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Environmental Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Health Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
Abstract
Air pollution problems are of the main environmental concern due to their
detrimental effects. Nitrogen oxides, sulfur oxides, carbon monoxide, carbon
dioxides, ozone, VOCs, unburned hydrocarbons, and particulate matters are
some of the most important air pollutants. These pollutants are emitted from
various stationary sources such as power plants, manufacturing facilities, indus-
trial boilers, and petroleum refineries. Mobile sources of air pollution include
motor vehicles, airplanes, locomotives, and ships. Oil, coal, and gas combustion
have the potential to change emissions from natural sources. Combustion of fossil
fuels is the main contributor to the air pollution. The exposure of air pollution has
many adverse effects to the environment and human health. Global warming and
depletion of ozone layer are the major environmental problems of the air
S. S. Kalender
Istanbul Technical University, Tirana, Albania
e-mail: sskalender@gmail.com
G. B. Alkan (*)
Barbaros Hayrettin Naval Architecture and Maritime Faculty, Iskenderun Technical University,
Hatay, Iskenderun, Turkey
e-mail: guler.alkan@iste.edu.tr

https://doi.org/10.1007/978-3-319-73645-7_77
150 S. S. Kalender and G. B. Alkan
pollution. Air emissions on land directly affect the acidification or eutrophication

of natural ecosystems and biodiversity of freshwater bodies concerning of sulfur
and nitrogen compounds deposition. Particulate matters have also negative
impacts on environment such as reduced visibility, light scattering, global
warming, accumulation on vegetation, change of ecosystem, and damage on
buildings and etc. On the other hand, respiratory illnesses, such as bronchitis,
asthma, and pneumonia, premature mortalities, cardiopulmonary disease, and
lung cancer are major health impacts of emissions.
Keywords
Air pollution · Emissions · Air pollutants · Air pollution problem · Health
effects · Environmental effects
Introduction
Parallel to the increasing population, the increasing number of vehicles in the traffic
and the air pollution problems of the big cities generally and industrial cities
specifically are causing some serious problems in the world we live today. Espe-
cially, in such large cities, the serious relationship between high levels of air
pollution and human deaths warns us of the severity of the problem.
When urbanization happens without serious consideration of climate and mete-
orological conditions, when green areas find little to no space at all in the cities, and
emission sources such as heavy traffic and industry blend undisciplined with the
living areas, the problems of air pollution in cities will approach the point of no
return. Urban sprawl can change the local and regional climate by affecting meteo-
rological parameters, thus causing changes in air quality.
Air pollutant is the generic name of all the substances that change the natural
composition of air. Natural clean air consists of gaseous components such as oxygen,
nitrogen, argon, carbon dioxide, hydrogen, neon, helium, krypton, and xenon.
Natural composition of air may contain water vapor and traces of other gases such
as methane CH4, ammonia NH3, carbon monoxide CO, and nitrogen oxide NO
resulting from decomposition processes and traces of ozone, possibly as a result of
stratospheric penetration (Baumbach 2012). The concentration of these chemical
species is usually less than one part per million of air by volume (1 ppm) and are
called trace gasses.
Air pollutants emitted into atmosphere, despite their countless sources, are
chemically unstable reagents and enter into chemical reaction with the other natural
gaseous components of the atmosphere. What makes the problem worse is the
dispersion factor of the atmosphere and the capacity of gaseous components to
travel long distances from their sources. The medium in which the air pollutants
are transported, atmosphere and its dynamics determines the life cycle and the
impact of air pollutants on the environment and humans. Many of these anthropo-
genic and xenobiotic chemical compounds defined as toxic or potentially harmful
are currently part of the biosphere. These chemical components either in their
6 Air Pollution 151
gaseous or in their particulate matter form have the potential to produce changes in
the environment and even the climate of our planet along with direct implications to
human health.
During the last century, the concentration of ozone (O3), nitrogen oxides (NOx),
sulfur, and organic particulate matter, as well as carbon dioxide (CO2), has increased
considerably with potential implications for the climate (Lazaridis 2011). Global air
pollution is mainly sourced by exhaust emissions from motor vehicles, industrial
facilities, and fuel consumption used in residential heating. Rapid urbanization and
increased energy consumption, especially in developing regions, turn out to be some
of the major pollutant factors.
It is important to take the necessary precautions, and in time, for the welfare and
happiness of the global society. The reluctance of some international actors or
societies to comply with the internationally agreed norms, despite them norms
being minimal, makes it increasingly difficult to deal with air pollution and its
ramifications on time.
Types of Air Pollutants
Air pollutants are often classified into three groups. NOx, SO2, CO, O3, and VOC are
the gaseous pollutants. Particulate matters (PM) are the other main group of air
pollutants.
Heavy metals such as lead, nickel, cadmium, and mercury are the pollutants that
occur little in the air, and therefore they are called trace elements. Nitrogen dioxide
(NO2), sulfur dioxide (SO2), ozone (O3), carbon monoxide (CO), particulate matter
(PM), and lead (Pb) are the main air pollutants stated by United States Environmen-
tal Protection Agency which has set US national air quality standards.
Carbon monoxide (CO), Nitrogen dioxide (NO2), sulfur dioxide (SO2), and lead
(Pb) are emitted directly from a variety of sources. Ozone is not directly emitted but
is formed when oxides of nitrogen (NOx) and volatile organic compounds (VOCs)
react in the presence of sunlight. PM can be emitted, or it can be formed when
emissions of NOx, sulfur oxides (SOx), ammonia, organic compounds, and other
gases react in the atmosphere.
Nitrogen oxides are formed when the oxygen and nitrogen mixture in the air
exposed to high temperatures during the combustion process. NO and NO2 are the
most harmful nitrogen oxides in terms of human health. Around 90–95% of the
nitrogen oxides formed during combustion are NO. Nitrogen oxides are oxidized in
the atmosphere and then nitrogen dioxides are formed. These nitrogen dioxides
cause secondary pollutants as a result of many reactions. In addition to temperature,
the formation of NOx depends on air-fuel ratio, pressure, and combustion time
within the cylinder, chemical reactions not being instantaneous.
The fuels used in diesel engines contain some sulfur. These sulfur compounds
burn during combustion period afterwards sulfur dioxide is formed. Sulfur trioxide is
formed in consequent reaction of oxygen and SO2. SO2 and SO3 gas sulfuric acids
react with some water and liquid sulfur sulfide (H2SO3) and sulfuric acids (H2SO4)
are formed. Sulfur oxide emissions mainly depend on the amount of sulfur present in
the fuel.
Carbon monoxide is an inevitable consequence of combustion. Therefore, CO
emissions are found in all exhaust gases such as in vehicle exhausts, fireplace
emissions, industrial smoke stack emissions, and in all internal combustion engine
emissions. Despite CO being an invisible, odorless, tasteless, it is a very toxic gas. Its
major mechanism of harm is binding with hemoglobin in the blood which is the
principal oxygen-carrying compound, resulting in a condition known as hypoxia. In
addition to the adverse effects on health, CO hurts the economy by causing diesel
engines and gas turbines notable heat and as a result, efficiency losses.
The formation of hydrocarbon emissions occurs when there is no complete
combustion in the cylinder. Fuel injection system problems in diesel engines are
the main reason of hydrocarbon emissions. Unburned hydrocarbon emissions mostly
depend on engine speed and load.
Particulate matters are the organic and inorganic particles suspended in the
exhaust gas. Particulate matters originating from diesel engines consist of organic
and elemental carbon particles, volatile organic compounds, ash, sulfate, and nitrate
particles. Particles that are released directly from the emission source to the atmo-
sphere are called primary particles; particles exposed to some chemical reactions in
the atmosphere condense and holds to the surface are called secondary particles
(EPA 2009). Most of the particulate matter consists of incomplete combustion of
hydrocarbon fuels. It is also caused by the combustion of some lubrication oil in the
engine (Heywood 1988).
Volatile organic compounds (VOCs) include organic compounds and mostly
aromatics such as olefins and paraffins. Main sources of VOCs are oil refineries.
Ozone is generated from various sources such as hydrocarbons emitted from
vehicles and even from terpines emitted by trees. These sources react photochemi-
cally with NO within the presence of ultraviolet radiation from the sun to make
gases. Ozone concentrations therefore are often found many kilometers downwind
from the main locations of sources, the interstate highways, and alternative engorged
roadways. Another issue that impedes ozone concentrations from constructing near
sources is the extremely complicated photochemistry concerned in ozone
production.
Ozone exists in the atmosphere in two distinct tectonic zones, the troposphere and
the stratosphere. Within the stratosphere, stratospheric ozone is found naturally at a
height of about 10–50 km from the ground and forms 90% of total ozone in the
atmosphere. Ozone in the stratosphere is also called benign ozone, because it pro-
tects the world’s vitality from the harmful effects of sunlight. At this layer,
ultraviolet-B (UV-B) rays, which constitute a major threat to the creatures on the
surface, are absorbed by ozone in the stratosphere layer. The second is tropospheric
ozone, which is human-originated, forming about 10% of the total ozone in the
atmosphere, about 10–15 km above the ground. Ozone in the troposphere is defined
as pollution if it has harmful effects on human health. Earth-level ozone is formed by
the effects of the sunlight, the complex chemical reactions of nitrogen oxides, and
volatile organics released into the atmosphere. For this reason, nitrogen oxide and
6 Air Pollution 153
volatile organic pollutants are also defined as ozone precursor pollutants. Methane
and carbon monoxide gases on the global scale can also cause ozone formation.
The heavy metals lead, mercury, and cadmium are common air pollutants, being
emitted principally as a result of numerous industrial activities (WHO 2007). After
they are released from anthropogenic and natural sources, they will travel long
distances and move the atmosphere. They deposit ashore or over water and reach
plants or fish and enter the organic phenomenon. Lead is the major additive to boost
the amount of fuel, and alternate octane raisers had to be developed as lead was
phased out, after it was found out that lead within the engine exhaust was an
extremely toxic pollutant (Pulkrabek 1997).
Sources of Air Emissions
Air pollutants are classified into primary and secondary according to their formation.
Primary air pollutants enter the atmosphere directly, whereas secondary pollutants
form by chemical reactions that involve different pollutants. Primary pollutants such
as NOx, SO2, CO, Pb, and particulate matters are emitted directly into the air.
Sources can be also different, anthropogenic, biogenic, geogenic, or some combina-
tion thereof. Once within the atmosphere, they are subjected to dispersion and
transport, i.e., exposed to meteorological activity, and at the same time to chemical
and physical transformations into gaseous and particulate. Secondary pollutants are
shaped from reactions of the primary pollutants in the air. Both primary and
secondary pollutants are removed at the earth’s surface via wet or dry deposition
and in the processes of transport, transformation, and deposition (Pitts and
Pitts 2000).
A polluting substance can be a solid, liquid, gas, or submolecular particle and
may originate from a natural or an anthropogenic source, or both (Sher 1998).
The most important anthropogenic source groups of air pollution are industrial
furnaces and industrial processes, traffic, small-scale businesses, and domestic
furnaces, as well as special sources such as animal confinement systems, spray
cans, etc.
Furthermore, gaseous and particle emissions occur from the Earth’s surface.
Specifically, the surface may be an enormous particle source into the atmosphere
because of particle suspension. Gaseous pollutants are emitted from the surface at
much lower rates than particles. However, natural emissions of nitrogen oxides
(NOx) from the surface could contribute considerably to the nitrogen oxides level
within the atmosphere and specifically in rural areas. As an example, emissions of
nitrogen oxides (NOx) from the Earth’s surface comprise 16% of the whole concen-
tration within the troposphere at global level. The Earth’s surface emits nitrogen
oxides through biological processes (bacterial processes) (Lazaridis 2011).
Anthropogenic air pollution has high exposure levels. It is produced in places
where people live. Additionally, it worsens the atmospheric conditions, and it affects
the environment adversely in many aspects. Because they can produce as explained
above unknown pollutants, there are regulations for anthropogenic emissions.
A major proportion of the pollutants caused in these diverse areas have its origin
in combustion processes, either in industrial and domestic furnaces or in traffic from
combustion engines and aircraft engines. Combustion of fossil fuels is the main
contributor to the air pollution. The fossil fuels gas, gasoline, fuel oils, and coals are
mainly comprised of hydrocarbon compounds with variable C/H ratios. Through the
combustion processes, carbon within the fuel reacts with oxygen to become carbon
dioxide, then hydrogen to become water. Lack of air causes incomplete combustion
with higher pollutant emissions (Baumbach 2012).
Stationary sources of air pollution are power plants, manufacturing facilities,
industrial boilers, and petroleum refineries. Mobile sources of air pollution include
motor vehicles, airplanes, locomotives, and ships. Anthropogenic air pollution
changes depending upon such factors as the industrial development of the region,
population, and urbanization status.
Effects of Air Emissions
Air pollution has many negative effects on visibility, materials, plants, animal health,
and especially human health. Smoke is a gaseous mixture of solid and liquid
particles that form from the lack of combustion of carbonaceous substances such
as solid fuels and fuel. It is a major source of air pollution and has an effect of
reducing visibility.
Air pollution has a destructive effect on historical and architectural constructions.
In certain cases, it has adverse effects on plants; it prevents plants growth and even
can cause death of the plants. For these reasons, air pollution is detrimental to all
living creatures and economy as well. Depending on the area humans live, because
of inhalation of high amounts of harmful substances in the atmosphere, the effects of
air pollution on human health are visible. The air we inhale must be free of pollutants
so that we can live well and comfortably. In other words, the inhalation of polluted
air, especially those that disrupt and pollute the air’s natural structure, can be
particularly destructive and lethal to lung tissues. Particles and smoke in the air
taken by the respiratory tract is swallow up during the inhalation and reaches the
lungs.
Environmental Effects
Air pollution has a widespread effect on living and nonliving organisms near the
sources of pollution or hundreds of kilometers away from the sources. Although the
concentration of contaminants released from the source of any pollutant to the
atmosphere may decrease, the distance from the source increases and may fall
below the threshold level that may cause harm. It may still have detrimental effects
at distances too far from the source, depending on the atmosphere and meteorolog-
ical conditions. For this reason, air pollution has environmental impacts at local,
regional, national, and international aspects. The environmental effects of pollutants
6 Air Pollution 155
depend on the characteristics of the pollutant source, the type and amount of
pollutants, and the characteristics of the emitting and the receiving environment.
In general, the environmental impacts of air pollutions are categorized as: effec-
tive on plants and animals, effective on materials and constructions, and effective on
atmosphere, soil and water resources.
Global Warming
The greenhouse effect is mainly due to the concentration of water vapor, CO2, and
alternative trace gases within the atmosphere. These gases absorb the terrestrial
radiation reflecting from the surface of the earth and acts as a sort of blanket over
the earth’s surface, keeping it warmer than it naturally is or needs to be. Changes
within the atmospheric concentration of those gases will change the balance of
energy transfers between the atmosphere, space, land, and also the oceans. A
gauge of those changes is termed the radiative forcing, that could be a measure of
changes within the energy obtainable to the Earth–atmosphere system. Holding
everything constant, the increase in greenhouse gas concentrations within the
atmosphere can turn out to be a positive radiative force (Muralikrishna and
Manickam 2017).
While the greenhouse effect created by air pollution has a great impact on world
climate through the “global warming,” it also causes detrimental environmental
results, such as drought and acid rain. Climatic disorders, which are alleged to be
happening, lead to extreme precipitation and flood disasters in different geographical
regions of the world. Air movements such as storms, hot air waves, and floods have
become the most common climate events nowadays.
Greenhouse gases that occur both naturally and from human activities include
water vapor, carbon dioxide (CO2), nitrous oxide (N2O), methane (CH4), and ozone
(O3). Chlorofluorocarbons (CFCs), bromofluorocarbons (halons), hydrochlorofluor-
ocarbons (HCFCs), hydrofluorocarbons (HCFCs), nitrogen trifluoride (NF3),
perfluorcarbons (PFCs), and sulfur hexafluoride (SF6) are the other greenhouse
gases.
Among several effects, a major one will result in a global warming of the earth’s
surface. Raised radiation of daylight on the surface, particularly of high-energy
ultraviolet radiation light, heats the surface of the earth as additionally reduced
light-weight reflection from the world of the lower atmospheric layers. Therefore,
at this point, it is time to additionally mention the destruction of the stratospheric
ozone layer because of the increase of the supposed greenhouse gases. Increases in
temperature will cause various and dreadful consequences, among them the shifting
of climatic zones and with them the shifting of the livable regions of the Earth.
Additionally it will cause expansion of the deserts and the flooding of larger areas of
land, thanks to the melting of polar ice masses (Baumbach 2012).
The layer of dirty air that forms on the cities causes the loss of ultraviolet rays, and
therefore it leads to decreases of the daylight. Such adverse events indicate the
deterioration of air pollution on natural climate balance. The effect of air pollution on
climate is twofold, one being local and the other worldwide. At the local areas, the
pollutants reflect, disperse, and at least absorb the sun lights which reach the surface
of earth. These events cause meteorological changes in the region. Such settlement
areas changes remain small on the worldwide scale, and hence meteorological
changes are on the lighter side of the scale of effects. Global pollution is on the
large scale is more important, because it affects the whole world.
Global warming has been attributed to greenhouse gases, such as water vapor,
carbon, methane, nitrogen dioxide, CFCs, and so forth, over the past 50 year. It is
estimated that the average temperature of world will increase from 1.4 C to 5.8 C
over the next century. The main prediction of this global warming is the increased
carbon dioxide emission by industries and vehicles (Wang and Corbett 2007).
The increase of the amount of greenhouse gas emitted to the nature, the destruc-
tion of the forests of the earth, the increase of the amount of radiation radiated by the
sun, the explosion of Gamma radiation, the depletion of ozone layer, the destruction
on natural areas for the reasons of agriculture and settlement, the emergence of
methane gas, which is a carbon derivative, as a result of the melted ice layers in the
ice covered tundra at the north of Russia, are the causes of the global warming.
Because the greenhouse effect changes the average temperature of the earth’s
surface, it can cause very serious problems such as changes in long-term climates,
melting of glaciers, and shifting of seasons and inefficiency of agricultural areas.
With the warming, more water will evaporate from the oceans and seas, and the
world will be more humid. This will cause an increase of precipitation. The amount
of rainfall on continents has increased by 1% over the last century. As the global
climate changes, the water level in the sea increases and the evaporation becomes
faster. With increased evaporation, precipitation will increase causing flooding and
landslides. The melting of glaciers leads under the effect of the global warming will
turn into an increase in the level of seawater, which in turn affects fresh water
reserves, especially in river outfall. The increase in atmospheric greenhouse gases
will lead to serious reductions in drinking water ratios as a consequence of acid rains.
Global warming will have various additional effects due to the decrease of water
resources. It will affect agricultural activities negatively, decrease the potential of the
energy, and as a result of these, social and economic problems will occur.
Either the increase in evapotranspiration (sweating and evaporation) or the
decrease in precipitation and changes in the precipitation regime will increase the
risk of drought in many regions. The changes in water resources will cause changes
to the living conditions of the living creatures in the ecosystem. Hurricanes will
probably be even stronger due to the evaporation of the water. Under the effects of
global warming, animals and plants will migrate to the poles and along mountainous
regions to higher altitudes. However, the generations of plant species that enwrap the
cities or agricultural land that are blocking these migration routes will be exhausted.
Changes resulting from global warming will affect the food resources of animals and
poses a threat to the very existence of living creatures.
Rising air temperatures due to climate change will increase the concentration of
the basic air pollutants such as ozone, sulfur dioxide, carbon monoxide, nitrogen
dioxide, lead, and particulates. As a result of this, human health in urban areas will be
under threat by the increase of the concentration of pollutants in air. It has been
recently estimated that future climate change, if left unaddressed, is expected to
6 Air Pollution 157
cause roughly 60,000 deaths globally in the year 2030 and 260,000 deaths in 2100
due to the effects of climate change on global air pollution by the a new study of the
University of North Carolina at Chapel Hill.
Depletion of Ozone Layer

Ozone happens naturally within the higher layer of atmosphere (stratosphere) and
also the lower atmospheres (troposphere). Ozone in the stratosphere protects the
earth from the sun’s radiation; ozone within the troposphere, however, will have
adverse health effects and other negative environmental impacts. The greenhouse
gases are water vapor, CO2, NO2, CH4, and chloroflurocarbons (CFCs); these gases
contribute the increasing and inflicting global warming. CFC gases destroy the
ozone within the stratosphere and therefore reduce the ozone layer’s radiation
protection. The stratospheric ozone, which provides protection from the sun’s
radiation, is named “good ozone,” whereas the tropospheric ozone, which is harmful
to human health and welfare, is named “bad ozone.” For our health or long-term
survival, we must protect the stratospheric ozone within the ozone layer. CFCs are
the first and foremost ozone-depleting substances. Other ozone-depleting substances
that conjointly reach the stratospheric ozone layer embody carbon tetrachloride,
methyl chloroform, and halons (Wang et al. 2004). In the higher stratosphere, ozone
happens in high concentrations. This natural ozone layer behaves as a filter for high-
energy daylight, as ozone has robust absorption bands within the ultraviolet radiation
range. The sunshine energy absorbed by ozone then becomes free of direction and is
then mirrored with a larger wavelength, as a result only a part of the sunshine energy
reaches the earth.
There is a critical point for the ozone gas in the atmosphere. Ozone gas forms a
layer in the upper layers of the atmosphere and this gaseous layer filters the lethal
rays from the sun. In this regard, the amount that reaches to the earth turns into a
useful form of sunrays energy for the existence of the livings. However, in the case
of this gaseous layer depletion, it cannot perform the expected functions, and the sun
rays become a real danger to the living creatures. Because of the variety of anthro-
pogenic air pollutants, ozone layer could be destroyed. The results would be a
warming of the Earth, increased UV radiation in the troposphere, and a decreased
stability of the thermal layering of the stratosphere. Humans, several animals, and
plants are sensitive to exhausting UV-B and UV-C radiation which carry even higher
levels of energy (Baumbach 2012).
Exhaust gases react photochemically in the sunlight and produce nitrogen dioxide
in the clouds of dirty air, resulting in ozone pollution in the lower parts of the
atmosphere near the earth. Symptoms of exposure to ozone pollution are irritations
in the eyes, nose, and throat, altogether resulting into major problems for the
respiratory system. It all leads to mucosal irritation and reduction of lung alveoli
flexibility. Ozone is a dangerous gas with a pungent odor. Even 2% of a gram has
fatal effect. It is poisonous and explosive even at very low concentrations.
Chlorofluorocarbons (CFCs), produced for various purposes, reduce the ozone
layer and thus they affect the environment and human health adversely. Ozone
molecules show different characteristics according to the location they are found
in the atmosphere. Ozone is useful to the livings when in the stratosphere, while it
has a destructive effect when found in the lower atmospheric layer (troposphere)
near the earth’s surface even when the amounts are as low as 10%. The ozone
reacting with other molecules in the troposphere causes plant and animal tissue
damages. Approximately, 90% of the ozone in the atmosphere exists at a height of
10 to 40 km from the earth and coinciding with the stratosphere layer. The charac-
teristic of ozone in this layer is the absorption of negative effects of ultraviolet
(UV) rays that affect all living things, natural resources, and agricultural products. If
the ozone concentration becomes any thinner, it cannot hold ultraviolet rays resulting
in a condition known as ozone depletion. As a result of the depletion of the ozone
layer; UV-B radiation is increasingly damaging human’s immune systems, major
problems being visual impairment and skin cancer.
UV rays also impact marine ecosystems negatively. It severely affects the plank-
tons that form the foundation of aquatic food network. One of them is Phytoplankton
flouris that grows close to the water surface and plays an important role in the food
chain and carbon cycle of ocean. It is well known that changes in UV levels affect
both orientation and movement in phytoplankton. In addition, these changes reduce
the survival and growth rate of these organisms.
Increases in UV radiation change the amounts of greenhouse gasses such as
carbon dioxide, carbon monoxide, ozone, carbonyl sulfide, and others. Variety of
UV levels can lead to biosphere-atmosphere feedbacks that mitigate or enlarge the
atmospheric concentrations of these gases.
Such concerns have been voiced in different levels, locally, nationally, even
internationally, and have found their way into different conventions. One such
important convention is the Kyoto Protocol concerning substances that affect the
depletion of ozone layer. The objective of the Kyoto Convention is to ensure that
the density of greenhouse gases in the atmosphere is balanced so that the climate
should not be endangered. The Kyoto Protocol is the only international framework
for the fight against global warming and climate change. Countries signing this
protocol have pledged to reduce emissions of six greenhouse gases (carbon
dioxide, methane, nitrous oxide, sulfur hexafluoride, HFCs, and PFCs) causing
carbon dioxide and greenhouse effect. If they can not manage so, they pledge to
increase their rights through carbon trading. The Protocol requires countries to
reduce carbon emissions from their atmospheric emissions to the levels of 1990.
The Kyoto Protocol covers more than 55% of the world’s 160 countries and
greenhouse gas emissions.
Effects on the Ecosystem

Our Earth contains a wide range of ecosystems: forests, rain forests, grasslands,
coral reefs, riverine and lacustrine systems, wetlands being the main actors of
ecosystems. These systems pose a great diversity and functionality. Exposure to air
pollutants can affect the aforementioned systems chemically, physically, or
biologically.
Ground-level ozone can reduce to disposure the agricultural crop and commercial
forest areas. Many air pollutants produce a range of negative effects on aquatic
6 Air Pollution 159
ecosystems. Sulfur and nitrogen compounds cause acidification of surface waters by

means of hydrolysis. Airborne nitrogen and phosphorus species may also enrich
surface water, that changes pH, dissolved oxygen, and other characteristics. Tropo-
spheric ozone has little direct impact on the chemistry of waters, but it alters the
biodiversity by stressing bank and partially submerged plants or harming
air-breathing animals. Stress on aquatic ecosystems can be noticed with the least
bit of abstraction in scales. Giant and vulnerable systems will indicate the impact of
pollutant loading on ecosystem condition. This can be significantly true for coral reef
systems (Stern 2014).
On the other hand, air pollution affects the terrestrial ecosystem which
includes many species. Various species of flora, fauna, and microbes react
differently to the exposure to air pollutants. Ozone, nitrogen dioxide, sulfur
dioxide, peroxyacetyl nitrate (PAN), and fluorides are the main air pollutants
which are phytotoxic for certain types of plants (Hindawi 1970). Pollutants
reduce enzyme levels of these plants are impacting them biochemically. Air
pollutants effects on plants can be on visible symptomatic level. At such a
level, the appearance of healthy leaves will change. For broadleaf plants, the
color of the healthy leaf is well due to the normal cell structure in the various
layers. Deviations from this healthy appearance happen because of tissue col-
lapse and plants will show different degrees of lack of color. Airborne pollutants
have adverse effects by contacting the surface of plant leaves, clogging the
leaflets of the respiratory pores, entering the respiratory pores, and participating
in the carbon dioxide extraction. The dust (dust or crusted dust) that accumulates
on the leaf surface blocks the photosynthesis phenomenon (physically), because
it reflects the sun’s rays. In the dry air, the CaO particles placed on the leaf
surface are converted into Ca(OH)2 by combining with the water vapor, espe-
cially in coarse leaves. In the meantime, the increase in heat causes burns and
other damages on the surface of the leaf. The dusts settle around the lobes of the
respiratory pores (stoma) on the leaf surface and prevent their breathing. When
the air is dry, perspiration continues from the stomas which cannot be closed.
The plant leaf is damaged or dried off permanently from excessive water loss
(drought effect). The harmful effects of pollutants on plants vary depending on
the type and amount of pollutant as well as the duration of exposure.
Leaves and soil surface are both affected by acidification. Organic materials that
come down to the soil surface by leaf casting are broken down by soil animals and
microorganisms (bacteria and fungi). These decomposition products penetrate into
the depths of the soil with precipitation waters. They are retained by clay minerals
and cycled by the roots as plant nutrients.
The accumulation of heavy metals in grasses and grassland plants affects the
growth of plants, as well as the health of animals fed by eating these plants within the
context of the food chain. A typical example of this is lead. Contrary to oxides that
are emitted from exhaust gases, lead accumulations occurs on the soil and plants
prevalently. On the other hand, fluorinated compounds that accumulate in the
grasslands and on the ground or plants have negative impacts on the animal’s
skeletal system.
Acid Deposition
Air pollution emitted from industrial areas is carried several kilometers downwind
far from the pollutant sources. These pollutants are mainly products of combustion,
such as nitrogen and sulfur oxides. Either these particles and gases pollutants slowly
settle to the ground in dry type deposition or they are transferred from the air
throughout the formation of cloud particles, so carried to the ground by rain and
snow as wet deposition.
Acid rainfall affects the chemical structure and biological conditions of the soil. It
washes and transports the calcium and magnesium of the soil to further away or
lower layers by water. This results in a lower soil quality that in turn affects and
lowers the efficiency of the agricultural yields. The substances that mostly contribute
to the acidification of the soil are the sulfur compounds passing through the soil after
the accumulation in the atmosphere. Nitrogen compounds play a role in the acidi-
fication of the soil only when the amount of the plants is more than enough and
absorbs it. One of the most significant artifacts of acidification on environment is the
acidic humidity caused both directly and indirectly from industrial activities. Some
substances like mercury, cadmium, or aluminum, which fall into soil or lake beds,
can enter into reactions with toxic substances, so resulting in acidic reactions,
although they are considered to be insoluble under normal conditions. These detri-
mental substances can bear the toxic effects by reaching the plants, animals, and
human through the food chain or drinking water. Aluminum that moves into the soil
as a result of acidification is the responsible cause for the deterioration of the ability
of the tree roots to collect nutrients.
Acid rainfalls negatively affect microorganisms on the soil surface. Water
acidification slows down or destroys the activity of bacteria on the soil surface.
When this happens, the decomposition slows down and acid products (humus
acids) emerge. The soil is unable to remove the cations or anions that are
released after decomposition of the organic matter. Cations in the soil colloids
are displaced by H+ ions which are present in high amounts in the acid rain.
These cations are washed from the soil with leachate and the soil becomes poor.
Thus, the buffer areas of the soil also change over time and there is a shift
towards the aluminum buffer area. Unfortunately too, aluminum turns into toxic
component in plants.
Two more active components responsible in soil acidification are sulfur dioxide
and nitrogen oxides. They mainly cause acidification of the groundwaters, acidifi-
cation of the lakes and rivers, i.e., lowering the pH value below 7. In addition, soil
corrosion also occurs. Acidification also affects humans through the water we drink.
Furthermore, from the aquatic products in taken as food, the harmful substances are
transferred to humans’ bodies damaging them in the process. In particular, fish
contain high-content minerals under the influence of hydrogen ions.
Depending on the acidification of the soil, heavy metals accumulate in the plants.
Heavy metal accumulation is also unavoidable in animals fed with these plants.
Cadmium accumulation is particularly common, especially in the liver and kidney
tissues.
6 Air Pollution 161
In acidified lakes, most water plants are adversely affected. This result does not
arise only from a direct decrease in the pH of the water. The detrimental effect of
aluminum is apparently revealed by a decrease in the pH of the water. Along with the
disappearance of fish, the release of aluminum has been effective regarding the
decrease of pH. Similarly, the amount of cadmium, zinc, and lead in the water is
increasing over time. These, like aluminum, are harmful to plant and animal life
when their concentration in water reaches a certain level. These unwanted chemical
substances arising from any lake can be transported from one lake to another by a
stream of water. These changes in water chemical properties also affect their
biological properties.
Upon the disappearance of fish, there has been noticed an increase of the presence
of some insects. The reason for this is the reduction or disappearance of fish fed with
insects. For this reason, in one respect, acidified lakes are not biologically dead lakes.
The acidity in the lake shows seasonal differences depending on the water sources
and rainfall that feed the lake. Lakes and rivers have the highest acidity in the spring
season due to the acidic waters’ first time being poured into the lake following the
snow season. Besides, the acidity of the water increases with the rain in the autumn.
The majority of the big cities exhibit damaged buildings and monuments. His-
torical structures, buildings, open metal surfaces, paint coatings, and some plastics
have deteriorated because of sulfur dioxide and other acidic precipitations.
Effects of acidic deposition on human health include irritation and redness in the
eyes, as observed in acidic atmospheres. Acidic particles usually cause atmospheric
dispersion of sulfur dioxide and nitric oxides. Nitric and sulfuric acid adheres to
other particles (dust, soot, smoke, etc.). Direct inhalation of these particles causes
these acidic structures to go straight to the lungs. The dusts and gases of these acidic
structures may chemically cause bleeding in the humid and hot lung alveoli. Acid
rains also have indirect effects on people. Acid rains reduce the pH value in surface
and underground waters and affect the water quality negatively. Depending on the
effects of acid rain on surfaces and drinking waters, groundwater, soil, heavy metals,
plants, and fish, the use of these elements causes acidic storage in the human body
over the long term.
The effects of the acidification event can be detected close to the sources of
polluting elements, as well as thousands of kilometers away. Some of the rain
descends directly into the lakes and rivers, some into the ground, and some other
into the groundwater mixing with the ground waters. Certainly, some part of it
evaporates as well. When the water comes down to the surface where the density
of limestone is high, we notice a decrease in the acidification properties. When the
water remains in coniferous forest areas, it becomes even more acidic.
Eutrophication
Eutrophication is an important factor in water nutrients; it will accelerate the growing
of the algae and higher plants especially because of nitrogen and phosphorus
compounds. As such, it will disrupt the balance of livings in the water ecosystem
and cause undesirable deteriorations in water quality.
Eutrophication is directly related to the transformation of NOx and NH3 emissions

into nitrogen. Excess nitrogen adversely affects the biodiversity. Furthermore, a
series of undesirable events occurs by eutrophication especially in land waters.
Eutrophication causes the death of fish or other living creatures in the sea due to
the lack of oxygen. Depletion of oxygen is considered to be a critical lake manage-
ment problem often associated with eutrophication. Lack of oxygen affects some
organisms living in the deeper layers. Also, fish yields decrease because of the lack
of oxygen in deeper layers. Algae blooms and uncontrolled growth of other aquatic
plants is caused by the eutrophication. Upon the depletion of oxygen, some toxic
substances are produced. Invasions of jellyfish and other species, hypertrophic
formation of mucilaginous aggregates, and an increased frequency of toxic
dynoflagellate appearances are some other adverse problems of the eutrophication.
Air emissions of nitrogen oxides from power plants, cars, trucks, and other
sources contribute to the amount of nitrogen entering aquatic ecosystems. NOx
emissions cause excessive nutrients in water bodies due to the eutrophication.
Reaching extreme values of nitrogen nutrients ecosystem balance breaks down.
Atmospheric Haze
Air pollution causes precipitation, turbidity, reduced visibility, and atmospheric
haze. Atmospheric haze is the condition of reduced visibility caused by the presence
of NO2 or fine particles into the atmosphere. Such pollutants (fine dry, wet dust, or
salt particles) dispersed into the atmosphere despite not being visible on their own
when clustered cumulatively will diminish visibility. Dry haze particles are very
tiny; they are measured at about 0.1 mm. Wet haze particles are larger than dry ones.
When the size range of particles is from 0.1 mm to 1.0 mm in diameter, light
scattering occurs. The source of these particles can be anthropogenic or natural. If
the relative humidity is high enough, soluble particles (nuclei) can obtain water
vapor and grow into haze particles. Haze will scatter light weight from the rising or
setting sun in such a manner that produces bright light-weight beams. Dust, little
water droplets, or haze in the air at altitudes lower than clouds scatter sunlight,
making that region of the sky seem bright with rays.
The significant component of atmospheric haze is sulfate particles (especially
ammonium sulfate), in conjunction with varied amounts of nitrate particulate, which
in some areas will equal the sulfate. Other elements embody graphitic material, fine
ash, and organic aerosols. The sources of particles within the atmosphere may be
primary, directly released into the atmosphere, or secondary, shaped within the
atmosphere by gas-to-particle conversion processes. The primary sources of fine
particles are combustion processes, such as power plants and diesel engines. Power
plants with advanced control technology still emit substantial numbers and masses of
fine particles. The composition of those particles includes soot or carbonaceous
materials, V2O5, sulfates, and trace metals. Additionally, massive quantities of NO2
and SO2 are released to the atmosphere. The secondary source of fine particles within
the atmosphere is gas-to-particle conversion processes, considered to be a lot of vital
source of particles contributing to atmospheric haze. In gas-to-particle conversion,
gaseous molecules become transformed to liquid or solid particles (Stern 2014).
6 Air Pollution 163
Reduced visibility results from light scattering and absorption by atmospheric

particles and gases. Size of particles plays an important role on light scattering. If the
particles are tiny, the amount of light scattered in the backward and forward
directions is almost the same. Since the size of particle increases, more light leans
to scatter in the forward direction.
The impact of particulates on visibility is more sophisticated driven by the very
fact that particulates of various sizes are ready to scatter light with varying degrees of
efficiency. It is this scattering phenomenon that is accountable for the colors of haze
in the sky. The sky is blue as a result of blue photons, with their shorter wavelengths,
situated nearer the scale of the molecules that form up the atmosphere than are their
green and red counterparts. Therefore, blue photons are scattered a lot faster by air
molecules than red photons, and as a consequence, the sky appearance blue (Malm
1999).
When nitrogen oxides and organic compounds are exposed to sunlight, a series of
complicated chemical reactions occur to create two principal byproducts: ozone (O3)
and an aerosol that, among other things, limits visibility (Wang et al. 2004).
Atmospheric haze worsens the visual air quality and impedes the clarity, color,
texture, and variety of what we tend to see. Although reduction of visibility poses
like a visual issue concerned in viewing a scenic resource, it has a psychological
impact besides the fact that sunlight scattered from clouds affects the vegetations
as well.
Material Damage
Air pollution destroys artworks and historical structures affecting all kinds of
materials and constructions, causing loss of aesthetic and economic value.
Acid depositions erode the foundations of structures in the cities in the world,
instances of damaged invaluables, fountains, sculptures, and statues exhibited in
the open. Precious artworks made of limestone preserving their artistic value until
recently were damaged by the effects of acid rain. Most historic values of art and
culture have been polluted and have lost their visual attraction. Metal works have
been oxidized and have lost their durability. Besides the historical art and cultural
works, recently built structures are affected by air pollution as well. Metallic
roofing materials have been corroded by acidic gases and acid rain and have lost
their functionality. Especially, due to the air pollution in residential areas, buildings
are dirty, automobile paints and tires wear out quickly, and building materials loose
their durability. Air pollution affects mostly metals that are directly exposed to
acidic gases in the air, resulting in the phenomenon called atmospheric corrosion.
The most corrosive gas is sulfur dioxide. Nitrogen oxides, ozone, acid rain, and
acidic snow also cause metal wear. Iron, zinc, sandstone, limestone, plastics, paper,
leather, and textiles are the main materials affected by air pollution. The effect of
such air pollution is more visible in settlement or industrial areas than in rural
areas.
The damage to materials is less vital than human health and ecosystem effects;
however, the prices definitely have an effect on society’s welfare, threaten public
safety, and result in financial costs.
Health Effects
Air pollutants that adversely affect the human health have a number of disease-
triggering features such as poisoning, cancer, birth defects, eye infections
and irritations, respiratory disorders, heart diseases, asthma, bronchitis, and viral
infections. During short-term increased exposure to air pollutants, a variety of acute
health problems will occur. Increased concentrations of air pollutant parameters lead to
increased asthma attacks. Long-term exposure to pollutants results in chronic health
effects. Exposure to air pollution in the prenatal period leads to loss of neurological
functions. While ozone exposure causes permanent damage to the cerebellum, it also
causes damage to the central respiratory control. Diesel exhaust particles have been
shown to impair locomotor activity in vivo after birth (Genc et al. 2012).
Although adverse effects of pollution are observed even in healthy people, certain
sensitive groups are more easily affected and more serious problems arise. Elder
people are the most affected group. Decreases in physiological capacity and phys-
iological defense mechanism functions are more easily caused by air pollution than
in the normal age group because of the increase in chronic diseases. Young children
are another vulnerable group with a greater risk of depleting the defense mechanism
because of higher ventilation rates, per body mass unit, and more frequent contact
with the outside. Diseases that cause contraction in the airways as well as the age
conditions increase the sensitivity to pollutants. Studies have shown that as pollution
increases, diseases such as asthma and chronic obstructive pulmonary disease
(COPD) increase. Low living standards, such as crowded life, inadequate sanitation
(environmental hygiene), and inadequate nutrition, are also factors that affect pol-
lutant sensitivity. Those who live under these conditions are confronted with infec-
tious disease problems.
Depending on the concentration of nitrogen oxides in the atmosphere, it has been
found that there are many negative effects in the lungs at long-term exposures. It can
lead to structural changes in the lung tissue and may cause an emphysema appear-
ance. Long-term exposure to low-level concentrations leads to changes in cellular
level. It also reduces resistance to bacterial and viral infections.
The health effects arising from air pollution depend on exposure conditions and
duration, the pollution mixture, and also the exposure manner. Human exposure
arises each from anthropogenic and natural pollutant sources. Besides air pollution,
there are other exposures through which toxic chemical compounds harm the human
body, some arising from food and water uptakes and furthermore from dermal
absorption (Lazaridis 2011).
Inhaled sulfur dioxide is absorbed in the upper respiratory tract. As a result, the
symptoms of bronchitis, emphysema, and other lung diseases are displayed. Carbon
monoxide reduces the oxygen intake capacity of the blood. Due to the lack of
oxygen in the blood vessels, deteriorations occur at brain, heart, and other sensitive
organs and tissues. The exposure of volatile organic compounds causes acute and
chronic health complications. Low doses of VOCs lead to asthma and some other
respiratory diseases. At high concentrations, VOCs have a narcotic impact on the
central nervous system. Some VOCs cause deterioration of nervous system when
6 Air Pollution 165
they reach extreme concentrations. These toxic compounds cause respiratory dis-
eases as well as nervous system damage at high concentrations. Metals that are
enclosed in emitted aerosols and gases from completely different anthropogenic
activities like metallurgical fumes (Cd, Cr, As, Ni) have an effect on the heart and
exteroception canals. Additionally metals like Cd, As, and Ni may be carried by
proteins and transferred to the human tissues and principally to the urinary organ.
Arsenic affects the function of kidney, spleen, and liver (Lazaridis 2011). The
physical structure and chemical composition of the particulate matter is very impor-
tant for health. The smallest particles are of the greatest concern since they can reach
into the alveoli and into the blood. The smaller particles follow the inhale flow but
the bigger particles get stuck before they even get to the lungs. This is due to their
aerodynamic differences. Asthmatic persons and persons with chronic obstructive
pulmonary disease (COPD) as well as patients with cardiovascular diseases and
small children are the ones mostly subjected to adverse health effects of fine
particles. Especially, particulate component of exhaust emissions can cause cardio-
pulmonary disease, lung cancer, and respiratory illnesses such as bronchitis, asthma,
and pneumonia depending on the size, shape, and chemical activity of the particles.
Approximately, 0.8 million deaths per year worldwide from outdoor urban PM2.5 air
pollution will lead to 1.2% of global premature mortalities each year (Cohen et al.
2005). Another dramatic example is that exposure to PM2.5 concentrations in 2012
were responsible for about 432,000 premature deaths originating from long-term
exposure in Europe (EEA 2015).
Exposure to air pollution leads to increased hospitalizations and mortality levels,
especially associated with cardiovascular diseases such as myocardial ischemia,
heart failure, arrhythmia, and deaths from respiratory system diseases such as asthma
and lung cancer (Chen et al. 2008). Air pollution is responsible for 2.5% of deaths in
developing countries (Narayan et al. 2010). In the study conducted by the World
Health Organization, the total mortality rate increased by 6% with an increase in PM
concentration of 10 μg/m3 per year. This short-term increase of 10 μg/m3 has been
shown to cause lower respiratory tract diseases, coughing, increased number of
hospital admissions, and death (WHO 2006).
Cross-References

World
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Status of Particulate Matter Pollution in
India: A Review 7
Geetanjali Kaushik, Arvind Chel, Satish Patil, and Shivani Chaturvedi
Contents
Particulate Matter Pollution: Status in India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
Particulate Matter: Sources and Health Impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
Particulate Matter Pollution: Studies from India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
Control Measures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
Abstract
Particulate matter has been implicated in various respiratory, cardiopulmonary
diseases, and even cancer. Many Indian cities find place among the world’s worst
polluted cities. Rapidly growing Indian cities have high concentration of partic-
ulates which is attributed to automobiles, industries, biomass burning, and
resuspension of road dust. In most cases, this concentration even exceeds the
permissible limits set up by the regulatory agencies. High particulate concentra-
tion would make particularly the urban population vulnerable to various forms of
G. Kaushik (*) · A. Chel

MGM’s Jawaharlal Nehru Engineering College, Mahatma Gandhi Mission, Aurangabad,
Maharashtra, India
e-mail: geetanjaliac@gmail.com; dr.arvindchel@gmail.com
S. Patil
Department of Environmental Sciences, Dr. Babasaheb Ambedkar Marathwada University,
Aurangabad, Maharashtra, India
e-mail: sushshrey@rediffmail.com
S. Chaturvedi
Department of Chemistry, Indian Institute of Technology Delhi, New Delhi, India
e-mail: shivani.d123@gmail.com

https://doi.org/10.1007/978-3-319-73645-7_78
168 G. Kaushik et al.
respiratory diseases. The problem of particulate pollution is more complicated by

location meteorology and seasonal variation making some locations like Delhi a
pollution chamber. Therefore, cleaner air should be India’s focus for economic
growth with regard to benefits of longer lives and fewer incidences of PM-related
sickness. Better pollutant monitoring systems, public awareness regarding the
adverse effects of PM, efficient vehicle engines, use of cleaner fuels, etc. would
go a long way in mitigating the harmful effects of particulates.
Keywords
Particulate · Pollution · Respiratory diseases · Monitoring · SPM · RSPM
Particulate Matter Pollution: Status in India
World over air pollution is a public health problem. In 2012, air pollution was declared
as the largest environmental health risk with almost seven million deaths globally
attributed to it (WHO 2014). According to the Global Burden of Disease 2010 report,
it was estimated that particulate matter (PM) air pollution was responsible for about 6%
of deaths on a global basis (IHME 2013; Lim et al. 2012). India is an important country
in South Asia with a rapidly growing economy and a large but young workforce.
However, rapid industrialization and urbanization in the country have resulted in a
significant deterioration in urban air quality (Kulshrestha et al. 2009). Data from the
country’s major regulator the Central Pollution Control Board (CPCB), showed that
77% of Indian urban clusters clearly exceeded the National Ambient Air Quality
Standard (NAAQS) for respirable suspended particulate matter (RSPM or PM10) in
2010 (CPCB 2012). The nonrespirable portion of particulate matter is suspended
particulate matter (SPM) and together RSPM and SPM constitute the TSPM (total
suspended particulate matter). Another key estimate from WHO pointed that out of
20 world’s worst particulate air polluted cities, around 13 are in India including the
capital Delhi, which is the worst ranked city in terms of air pollution (WHO 2014). It is
quite alarming to note that the satellite measures of fine particulates created for the entire
India reveal that our populations living both in urban and rural areas are exposed to
hazardously high levels of particulates. Almost 670 million people comprising 54.5% of
the population reside in regions that do not meet the Indian NAAQS for fine particulate
matter (Greenstone et al. 2015; Dey et al. 2012). Numerous studies have revealed a
consistent correlation for particulate matter concentration with health than any other air
pollutant. Studies show a statistically significant correlation between mortality and
ambient particulate matter concentration (Lee et al. 2006). Therefore, it is necessary to
understand particulate matter, its sources, and health impacts.
Particulate Matter: Sources and Health Impacts
The term “particulate matter” (PM) refers to tiny particles which remain suspended
in air, in the form of either solid or liquid droplets which originate from various
sources that pollute the ambient air. Particulate matter comprises of various organic
7 Status of Particulate Matter Pollution in India: A Review 169
and inorganic components; the major components include acids, ammonia, sodium
chloride, black carbon, water, and mineral dust. The respirable particulates having
aerodynamic diameter 10 μm (PM10) are an important part of the atmosphere.
Six main sources of ambient particulate matter include: traffic, industry, domestic
fuel burning, natural sourcesincluding soil dust (resuspended) and sea salt, and
unspecified sources of pollution of anthropogenic origin. Traffic includes various
types of vehicles which in addition to primary PM emissions from exhaust and
emissions of organic and inorganic PM precursors from fuel andlubricants combus-
tion, considerable amounts of particles are emitted through the wear of brake linings,
clutch, and tires (Amato et al. 2009; Belis et al. 2013). These are deposited onto
the road and are then resuspended by vehicle traffic along with crustal dust particles.
Industry is a heterogeneous category including emissions from oil combustion,
coal burning in power plants, and emissions from different industries (petrochemi-
cal, metallurgic, ceramic, pharmaceutical, IT hardware, etc.) and from harbor-related
activities (Belis et al. 2013). Domestic fuel burning includes wood, coal, and gas
fuel for cooking or heating. Natural sources include soil dust and sea salt. Soil dust is
resuspended from fields or bare soils by local winds. Sea salt particles in the air can
be found close to the coast (Seinfeld and Pandis 2006). Unspecified sources of
human origin mainly include secondary particles formed from unspecified pollution
sources of human origin. Primary particle emissions include mechanically generated
particles and primary carbonaceous particles. Primary particles also include carbo-
naceous fly-ash particles produced from high temperature combustion of fossil fuels
in coal power plants. Secondary particles are formed in the atmosphere through
reactions of primary gaseous pollutants (nitrogen dioxide NO2, ammonia NH3,
sulfur dioxide SO2, nonmethane volatile organic compounds NMVOCs) (Belis
et al. 2013).
A total of 419 source apportionment records from studies conducted in cities of
51 countries were used to calculate regional averages of sources of ambient partic-
ulate matter. Based on the available information, globally 25% of urban ambient air
pollution from PM2.5 is contributed by traffic, 15% by industrial activities, 20% by
domestic fuel burning, 22% from unspecified sources of human origin, and 18%
from natural dust and salt (Karagulian et al. 2015).
PM is widespread and affects more people than any other ambient air pollutant.
These particles have a high probability of deposition deeper into the respiratory tract
and are likely to trigger respiratory diseases such as asthma, bronchitis, cardiopul-
monary infections (Greenstone et al. 2015; WHO 2014). Epidemiological evidence
has even attributed PM10 in cancer and in some cases even premature death.
The relative strength of association of air pollutants with mortality were reported
as follows: PM2.5 PM10 SO2 H+ O3 NOx(Dockery et al. 1992; Das
et al. 2006). Further it has been found that for each 10 μg/m3 increase in PM10
concentration, there is an estimated increase in mortality by almost 1% (Dockery and
Pope 1994; Ostro 1996; Das et al. 2006). Each 10 μg/m3 elevations in fine particulate
air pollution has been associated with approximately with 4, 6, and 8%increased risk
of all cause, cardiopulmonary and lung cancer mortality, respectively (Pope 2000).
These particles have also been implicated as carriers of toxic air pollutants
including heavy metals and organic compounds (Satsangi et al. 2011).
According to “National Ambient Air Quality Standards – 2009,”when PM10 parti-

cles are present in excess of 60 μg/m3(annual basis),these are known to adversely
affect human health. In view of the air quality status, some of the Indian cities
are considered to be among the most polluted cities in the world (Mitra and
Sharma 2002). It is well known that PM10 is a better indicator of total suspended
particulate matter (Das et al. 2006; Abba et al. 2003).
From the above discussion, it is evident that the presence of particulate matter in
the air is associated with various adverse effects on human health, other living
and nonliving components. It is therefore of significance to conduct monitoring
studies to estimate the concentration of PM in the ambient air so that public is aware
and can reduce its exposure. In addition, the government agencies and institutions
can undertake arrangements to protect the population from such adverse effects
of PM pollution (Kaushik and Borah 2016). In this regard, this chapter reviews
the status of PM pollution across India. It is expected that this chapter would provide
key insights into locations with high PM concentrations, need for mitigation and
policy measures for the government.
Particulate Matter Pollution: Studies from India
Table 1 summarizes the results of PM monitoring studies conducted across India.

For ease of understanding, India has been divided into North, West, Central, East,
and South India and the literature is summarized accordingly (Fig. 1).
Discussion
From the above background on particulate matter concentration from various loca-
tions across India, it is clear that barring few almost all locations have high PM
10 and PM 2.5 not only in commercial and industrial areas but also the residential
areas which has been attributed to automobiles, construction activities, industries,
and suspension of road dust. PM concentrations clearly exceed the national stan-
dards. Hence, urgent steps to reduce particulate matter concentration are warranted
to safeguard the health of consumers in particularly high PM concentration areas.
It is also evident that the four metropolitan cities are the focus of PM monitoring
studies particularly Delhi which has the maximum number of studies followed
by Kolkata, Chennai, and Mumbai. Next to follow are the studies on state capitals.
East part of India seems to be underrepresented in terms of monitoring studies.
Particulate matter pollution has not received due attention in the country which is
responsible for this grave situation. If we observe the CPCB data for Indian cities,
it is evident that almost 85 Indian cities fall in the category of critical with regard to
PM pollution (CPCB 2014).
When the CPCB 2014 data trends in air quality for states and union territories
(UT) are examined out of 31 states and UTs for four namely Dadra & Nagar Haveli,
Daman & Diu, Manipur and Sikkim there was no data available. Out of the
7
Table 1 Summary of PM monitoring studies across India

S. PM class and Time period of
No. Site State Typology concentration PM contributor measurement Reference
1. Daryagani Delhi, North Commercial PM10 Vehicular February – May Balachandran
India 658.45 μg/m3 emissions, 1998 et al. 2000
Jawaharlal Open space 454.77 μg/m3 industrial
Nehru emissions, and soil
University resuspension
Moti Nagar Residential 552.8 μg/m3
2. Rohini Delhi Residential SPM Construction Kannan and
111–2222 μg/m3 activities and Rajola 2004
excess road dust
3. 7 locations Delhi Residential SPM 280–420 μg/m3 Lifting of road 24 hourly annual Goyal et al. 2006
Industrial sites 300–450 μg/m3 dust, average levels 1987
meteorological to 2003
conditions,
anthropogenic
sources
4. India Gate Delhi Open space SPM decreased from Decline due to Ambient air quality Devi et al. 2007
Status of Particulate Matter Pollution in India: A Review
470 to 275 μg/m3 and integrated plan of 1999–2003

RSPM from 390 to Delhi Government
220 μg/m3 and CPCB
5. Bahadur Shah Delhi Busy traffic PM 2.5 concentration Continuous ambient CPCB 2006
Zafar Marg intersection μg/m3 air quality
214.8 winter monitoring
78.2 summer 2006–2007
70.5 monsoon
6. Urban centers Haryana 8 districts TSPM Different seasons Kaushik et al.
Residential, 158.3 μg/m3 (Sonipat) January 1999 to 2006
commercial, to 868.0 μg/m3 September 2000
industrial, and (Faridabad)
171
sensitive Commercial areas from

(continued)
172
Table 1 (continued)
191.3 μg/m3 (Hisar) to
1756.6 μg/m3
(Sonipat), in industrial
areas from 126.4 μg/
m3 (Panipat) to
1075.8 μg/m3
(Yamunanagar)
PM10 ranged from
32.0 μg/m3 in sensitive
area in Panchkula to
430.0 μg/m3 in
commercial area in
Sonipat
7. Mandi Punjab Industrial and Average PM10 in 10 months Nautiyal et al.
Gobindgarh nonindustrial town Mandi were 161.20 μg/ 2007
and Morinda m3
Levels in Morinda
were 99.54 μg/m3
8. Southern Delhi Delhi Industrial site PM 2.5: 126.7 3-week period Shandilya et al.
PM10: 268.6 24-h average 2007
Total suspended
particulates (TSP):
687.7 μg/m3
9. Haridwar Uttarakhand Residential SPM December Chauhan and
Industrial 380.41–413.91 μg/m3 2006–February Joshi 2008
510.38–522.29 μg/m3 2007
G. Kaushik et al.
7
10. Haridwar Uttarakhand Residential PM10 Chauhan et al.

Dehradun Industrial 98.47–141.28 μg/m3 2010
Commercial 160.80–175.78 μg/m3,
Agricultural areas 67.53–148.33 μg/m3
and 19.88–33.39 μg/m3
11. Ludhiana city Punjab Industrial, Annual mean RSPM Kumar et al.
commercial, and ranged from 226.7 to 2010
residential 269 μg/m3
12. Mayapuri Delhi Industrial RSPM 24 hourly average in Prakash and
Town Hall Commercial 62–664 μg/m3 2009 Bassin 2010
Sarojini Residential 48–619 μg/m3
28–483 μg/m3
13. Six sampling Rohtak SPM 8 h daily with a Shukla et al.
sites 354.93–1216.37 μg/m3 frequency of once in 2010
in summer to a week
404.54–1310.76 μg/m3
in winter and
245.14–915.91 μg/m3
in monsoon
14. New Delhi Delhi Averaged Geometric mean for Apte et al. 2011
autorickshaw concentration 190 μg 60

trip m3 PM2.5 autorickshawtrip
15. Sonamarg, Jammu & TSPM from 10 to Tourist activity July–December Jehangir et al.
Thajwas Baltal Kashmir 1250 μg/m3 and PM and vehicular 2009 2011
Kashmir valley 10 ranged from 15 to density
295 μg/m3
16. Delhi Delhi Industrial TSP- 687.71 October–November Kaushik et al.
Residential PM 10: 268.6 2000 2011
Commercial TSP-495
PM 10: 202.1
TSP-514.6
PM 10: 256.9
173
(continued)
Table 1 (continued)
174

17. Delhi and Delhi Residential PM 10 Traffic, industries, Weekly intervals Sharma et al.
Chandigarh Industrial Delhi: 192.88–288.8 thermal power Dec 2010–March 2012
Chandigarh: plants, and urban 2011
132.5–186.9 activities
18. Jammu J&K Residential areas SPM 2004–2005 Sharma and
Commercial 276.19–403.80 Raina 2013
Traffic crossings 485.48–788.49
711.75–1014.30
19. Meerut and National Industrial, SPM, RSPM 646 Monthly (8 hourly) Tyagi et al. 2014
Ghaziabad Capital residential, and μg/m3, 330 μg/m3 at data during July
Region commercial areas Sahibabad Industrial 2009 to June 2011
area, Raj Nagar
residential area:190 μg/
m3, 90 μg/m3
Begum Bridge,
Meerut: 543 μg/m3,
282 μg/m3
West India
20. Ajmer Rajasthan Industrial, traffic, RSPM Monthly and Chalka et al.
residential 488.0 μg/m3 in seasonal analysis in 2006
sensitive locations December and June at 2004
industrial site
21. Worli, Mumbai Maharashtra Ambient and PM2.5 and PM10 were Three seasons April Kumar and
kerbsite 43 and 61 μg/m3, 2003 to March 2004 Joseph 2006
respectively at ambient
site and at kerbsite, it
was 69 and 90 μg/m3,
respectively
G. Kaushik et al.
7
22. Pune city Maharashtra Average PM10 was Sampling was once Gidde 2007
120.35 μg/m3 in a week for
6 months i.e., from
June 2006 to
November 2006.
23. Udaipur city Rajasthan Residential, traffic, RSPM ranged from November 2007 to Kapoor et al.
and industrial areas 48.01 to 369.76 μg/m3 October 2008 2009
and its maximum
values varied
81.43–1032.1 μg/m3
24. Vashi, Navi Maharashtra Industrial belt PM2.5–10: 70 μg/m3 2008 Kothai et al.
Mumbai PM2.5: 41 μg/m3 2011
25. Jaipur city Rajasthan 12 sites in SPM varied between Winter 2009–2010 Kumar et al.
residential, 79.81 and 854.33 2011
industrial, μg/m3
commercial areas RSPM ranged
46.64–340.85 μg/m3
26. Udaipur Rajasthan Urban, industrial, SPM ranged between September 2010 to Kapoor et al.
forest areas 118.39 (rainy season) August 2012 2013
to 528.56 (summer
season) μg/m3
27. Udaipur Rajasthan Urban site PM2.5: 8–111 μg/m3 Daily from April Yadav et al. 2014
PM10: 28–350 μg/m3 2010 to March 2011
28. Udaipur Rajasthan Rresidential, In residential areas, Nair et al. 2014
urban, and SPM varied from
industrial areas 295 μg/m3 in August to
448 μg/m3 in
December. In urban
areas, it varied from
342 μg/m3 to 450
μg/m3 and in industrial
areas 335 μg/m3 to
175
592 μg/m3
(continued)
Table 1 (continued)
176

Central India
29. Indore Madhya 11 locations, Average RSPM range Joshi and Jain
Pradesh mostly at outer city 39.78–649.92 μg/m3 2000
areas
30. Jharia Jharkhand Work zone and High SPM, RSPM, Open cast coal Ghose 2002
coalfields surrounding high benzene soluble mining
Dhanbad locations matter and anions in
SPM
31. Lucknow city Uttar PM10 ranged between During summer Sharma et al.
Pradesh 107.6 and 237.8 μg/m3 2006
32. Kanpur Uttar PM10 ranged between During summer and Sharma et al.
Pradesh 359 and 169 μg/m3 winter 2006
33. Lucknow city Uttar Residential PM2.5 was Motor vehicle November 2005 Barman et al.
Pradesh locations 142.74 μg/m3 emissions 2008
34. North central Uttar Urban PM10: 154.2 μg/m3 Vehicular Three monthly 24-h Kulshrestha et al.
Agra Pradesh Rural site PM2.5: 104.9 μg/m3 activities, solid samples May 2009
PM10: 148.4 μg/m3 waste incineration, 2006–March 2008
PM2.5: 91.1 μg/m3 and industrial
emission at urban
site while
vehicular
emission,
construction
activities, and
wind-blown dust
carrying industrial
emission at rural
site
G. Kaushik et al.
35. Lucknow city Uttar 10 locations in SPM: 382.3 μg/m3 24-h average Barman et al.
7
Pradesh urban area and a RSPM: 171.5 μg/m3 in concentration in 2010

village area urban areas May 2006
36. Taj Mahal, Uttar PM10: 115–233, 24-h average in Singh et al. 2010
Agra Pradesh 155–321, and summer, winter, and
33–178 μg/m3 rainy seasons
37. Latur city Maharashtra Residential, RPM: 112 μg/m3, Six months from Muchate and
commercial, and 104 μg/m3, 70 μg/m3 June 2010 to Chougule 2011
industrial areas SPM: 210 μg/m3, December 2010
245 μg/m3, and 147 μg/
m3
38. Nagpur city Maharashtra Industrial area 100–254 μg/m3 Increased human 24-hourly average Chaudhari et al.
Commercial 54–225 μg/m3 population, values in 2006 2012
Residential 52–107 μg/m3 activity, and traffic
39. Lucknow city Maharashtra 4 locations PM10 and PM 2.5 Three different Pandey et al.
148.6–210.8, seasons 2012
32.4–67.2 μg/m3 Summer
111.8–187.6, Monsoon
25.6–68.9 μg/m3 Winter
199.3–308.8,
99.3–299.3 μg/m3
40. Nagpur city Maharashtra PM 10 and PM 2.5 Burning of Pre-Diwali, Diwali, Rao et al. 2012
were 930 μg/m3 and crackers and and post-Diwali
271 μg/m3 sparkles on Diwali
41. Raipur Chhattisgarh Annual average PM10, July 2009 to June Deshmukh et al.
PM2.5–10, PM2.5, and 2010 2013
PM1 were 270.5,
119.6, 150.9, and
72.5 μg/m3
42. Nashik city Industrial, SPM levels ranged Khandbahale and
commercial, and from 201 to 256 μg/m3 Saler 2013
residential areas being highest at
177
commercial areas
(continued)
Table 1 (continued)
178

43. Kanpur city Three major road Among all sites, Construction During summer and Kumar et al.
and railroad Kalyanpur with heavy activity winter seasons of 2014
intersections duty vehicles had the 2011
(TSPM) and PM10 highest PM10 (1110 μg
levels were m3), PM2.5 (124 μg
generally higher at m3), and PM1 (46 μg
vehicular m3) levels
intersections and
construction sites
44. Nagpur Maharashtra Annual concentration Anjikar et al.
of SPM was 270 μg/m3 2015
and of RPM was
150 μg/m3
45. Aurangabad Maharashtra Traffic intersection PM 10353.98 μg/m3 High traffic, poor December Kaushik et al.
Industrial 303.77 μg/m3 roads, construction 2015–January 2016 2016
Residential 208.86 μg/m3 activities
Commercial 255.66 μg/m3
East India
46. Jyotivihar Orissa SPM ranged from One year Sarangi and
82.99 to 182.7 μg/m3 Mishra 1997
47. Tantra- Orissa SPM ranged between Three different Das et al. 2003
Raikela- 91.9 and 338.9 μg/m3 seasons of the year
Bandhal iron 2000–2001 at six
ore mines locations
48. Korba Chhattisgarh SPM: 96–431 Coal burning and Summer and Singh et al. 2004
coalfield, PM10: 55–327 μg/m3 transport activities monsoon seasons of
SPM: 94–172 μg/m3 2003
PM10: 43–100 μg/m3
G. Kaushik et al.
7
49. Kolkata West Bengal PM10: 304 μg/m3 Winter of 2002 Das et al. 2006
PM2.5: 179 μg/m3 24-hourly average
PM10–2.5: 126 μg/m3
50. Kolkata West Bengal Residential and PM10: 140.1 and Vehicular traffic, From November Karar et al. 2006
industrial sites of 196.6 μg/m3 road dust and soil 2003 to November
an urban region Cr: 6.9 dust at residential 2004
Zn: 506.1 site
Pb: 79.1 Vehicular traffic,
Cd: 3.3 road dust,
Ni: 7.4 electroplating, and
Mn: 2.4 tanning industry at
Fe: 103.6 ng/m3 industrial site
51. Kolkata West Bengal Residential and PM 10: 68.2–280.6 μg/ Higher PM values Seasonal and spatial Karar et al. 2006
industrial sites in m3 in residential and at industrial area variations of PM 10
urban area 62.4–401.2 μg/m3 in due to heavy traffic
industrial area. High flow, emission from
PM 10 in winter and nearby industries
minimum in monsoon and resuspension of
road and soil dust
Higher winter
concentration due
to low winds and
low mixing heights
52. Choudwar Odisha Six stations located SPM found minimum Bhuyan et al.
area, Cuttack in rural area while (102.2 μg/m3) in rural 2010
district four stations area in monsoon 2007
located in
industrial belt
53. Dhanbad Jharkhand Mean annual PM10 at Coal mining Dubey et al.
mining and nonmining activities, diesel 2012
areas were 258 64 vehicle exhaust,
and 134 29 μg/m3,
179
(continued)
Table 1 (continued)
180

with overall mean of industries and
193 79 μg/m3 for biomass burning
Dhanbad
Mean Pb
concentrations were
0.024–0.32 μg/m3, Ni
0.002–0.02 μg/m3, and
Cu 0.06–6.32 μg/m3
while Mn varied from
0.14–1.9 μg/m3. Fe,
Zn, Cd, and Cr varied
from
1.43–28.48 μg/m3,
0.16–2.55 μg/m3,
0.03–0.07, and
0.11–0.42 μg/m3,
respectively
54. Kalinga Nagar, Odisha Industrial complex SPM maximum at Seasonal study Panda and Panda
district of Manapur and Duburi 2010–2011 2012
Jajpur square (7961.11 μg/m3)
in December 2010.
RSPM maximum at
Manapur in March
2011 SPM and RSPM
both lowest in
monsoon
55. Guwahati, Assam Residential and RSPM (μg/m3) for the Barman 2013
Dibrugarh, commercial areas years 2007, 2008, and
Golaghat, 2009
Guwahati:
G. Kaushik et al.
7
Tezpur, and 86.67–112.97,

Bongaigaon 94.74–149.57,
111.32–139.74
Golaghat: 71.35, 67.74,
and 61.2
Dibrugarh, Tezpur, and
Bongaigaon were
within limits
56. Rourkela Odisha PM10 from 80.88 Iron and steel 8-hourly average Kavuri and Paul
μg/m3 to 225.93 μg/m3 industry, fossil concentration of 2013
Fe: 102.14 ng/m3 fuels PM10 January 2011
Al: 50.53 ng/m3 and December 2011
Zn: 41.90 ng/m3
SO4: 1920 ng/m3
Heavy metals, anions,
PM10 showed a lower
concentration during
summer and monsoon
and higher during winter
57. Gopalpur, West Bengal Rural site close to PM10 ranged from Industrial February 2013–May Dey et al. 2014
Durgapur highway and 53.803 to 271.325 emission, 2013

industry μg/m3, with a mean vehicular
value of exhausts, open
136.689 54.873 biomass burning,
μg/m3 mining
58. Dhankheti Meghalaya RSPM, NRSPM, Varied from 81.24 to Motor vehicle April 2010 Lamare and
Junction, and TSPM 261.43 μg/m3; emission Chaturvedi 2014
Shillong City 73.17–265.54 μg/m3,
and 212.49–467.94 μg/
m3
59. Santipur, Assam Six stations in SPM ranged from Transportation, 8-hourly sampling Gohain and
Guwahati industrial, 282 to 491 μg/m3, industries, and on all working days Kalita 2016
181
(continued)
Table 1 (continued)
182

commercial, and 85–206 μg/m3 and high rate of of a week April,
residential areas 74–146 μg/m3 combustion of May, and June 2014
RSPM from 153 μg/m3 conventional fuels
to 236 μg/m3, 33 μg/
m3–107 μg/m3, and
44 μg/m3–89 μg/m3
South India
60. Bangalore city Karnataka Ten congested SPM values exceeded Vehicular emissions Dayal and
areas prescribed limits in six and ambient air Nandini 2000
of the ten congested quality for 14 days
areas
61. Coimbatore Tamil Nadu Eight sites were SPM higher than Detailed survey at Meenambal and
city residential and threshold limits in main ten important Akil 2000
rural mixed zone, traffic routes and junctions
one industrial and commercial localities
one sensitive zone
62. Madurai city Tamil Nadu SPM: Winter season in Raja Mohan
295.8–385.7 μg/m3 1999 2000
Pb: 0.31–0.84 μg/m3
63. Visakhapatnam Andhra 16 stations High SPM levels in Postmonsoon Suneela and
Pradesh industrial as well as season Thakre 2000
some residential zones (October–January
1998)
64. Cochin City Kerala Industrial, SPM 700, 790, and 12 samples of 1-h Anto 2001
residential, and 900 μg/m3 duration in
commercial sites 1997–1998
65. Tiruchirapalli Tamil Nadu Four residential SPM between 48.08 Fireworks Festival of Diwali in Ravichandran
city sites and 871.27 μg/m3 1997 et al. 2001
G. Kaushik et al.
7
66. Madurai city Tamil Nadu Industrial, traffic, SPM in summer Six sampling Samy 2003
residential, and 144.5–359.4 μg/m3 and stations
sensitive zones in winter between
154.9 and 282.4 μg/m3.
Pb in summer varied
from 0.21 to 0.64 μg/
m3 season, and in
winter from 0.22 to
0.74 μg/m3
67. Coimbatore Tamil Nadu Urban and RSPM levels ranged Vehicular traffic Six sampling Mohanraj and
suburban between 30 and 149 μg/ and traffic locations Azeez 2005
m3 congestion
68. Madurai Tamil Nadu PM10 varied from 88.1 Bhaskar et al.
to 226.9 μg/m3 and 2008
lead ranged between
0.21 and 1.18 μg/m3
69. Chennai Tamil Nadu Residential 105.58–128.17 2000–2002 Senthilnathan
Traffic 351.50–399.25 2008
70. Madurai Tamil Nadu PM10 varied from 97.2 One year at six Bhaskar et al.
to 152.5 μg/m3 locations 2010
Industrial areas had
highest concentrations
of heavy metals such as
Fe, Zn, and Cr and also
the SO24 ions
Traffic areas had
highest concentrations
of Cd and the NO3 ion
(continued)
183
184
Table 1 (continued)
71. Shivmogga Karnataka Five different SPM varied from 516.2 High traffic June–October 2009 Patel et al. 2010
city locations to 1005.5 μg/m3 volume,
construction of
buildings and
flyovers
72. Hyderabad city Andhra 40.9–499.5 μg/m3 for June 2004 to May Gummeneni
Pradesh PM10 and 2005, PM2.5 and et al. 2011
31.1–285.5 μg/m3 for PM10 measured at
PM2.5 15-min intervals by
the Punjaguta online
monitoring station
73. Port Blair – SPM ranged between November Jha et al. 2011
35 and 174 μg/m3 2007–January 2008
74. Warangal Andhra Residential RSPM Vehicular 45 days Shashidhar et al.
Pradesh Commercial and 50 μg/m3–70 pollution and 2011
traffic 160 μg/m3–180 human activities
Sensitive 100 μg/m3–160 μg/m3
75. Puducherry – Eight sites with SPM ranged Transport and civil 8h Balashanmugam
heavy traffic and 252.63–388.72 μg/m3 construction et al. 2012
commercial activities
activity
76. Chennai Tamil Nadu Industrial, Annual average PM10 Gajghate et al.
commercial, and levels varied from 32 to 2012
residential 48 μg/m3
locations Cd, Zn, Pb, Fe, Ni, and
Cr are higher in
industrial sites
G. Kaushik et al.
7
77. Salem Tamil Nadu Annual mean TSPM Vehicular traffic, 8-hourly sampling Gunasekaran
was 110.5 μg/m3 gen-set operations, with a frequency of et al. 2012
RSPM was 74.4 μg/m3 and emissions twice a week, April
from the nearby 2010 to March 2011
steel alloys,
medium scale
units, resuspension
of traffic dust
78. Hosur town Tamil Nadu Three chosen sites PM10 varied between Harikrishnan
busy roads 45 and et al. 2012
intersections and 127 μg/m3 PM2.5
bus terminals higher at all three
locations
79. Dindigul Tamil Nadu Residential SPM Construction, road Bimonthly for year Prathipa et al.
Traffic 460.2 dust 2015
Industrial 550.2
667.2
185
Fig. 1 India’s map with major monitoring locations
remaining 27, a whooping 24 states and UTs exceeded the standards. This clearly
highlights the grave situation the country is facing and urgent steps are warranted for
its mitigation.
From the above background,it is quite evident that PM concentrations are greater
due to greater emissions from variouspollutant sources;however, the particulate
concentrations may be elevated due to other reasons such as meteorology.
The meteorology of the location plays an important in determining the pollutant
load. Numerous studies have assessed the influence of wind speed, wind direction,
rainfall, relative humidity, and temperature on particulate matter pollution.
The measured PM pollution generally showed inverse relationship with wind
speed, relative humidity, and temperature (Karar et al. 2005). Therefore, it is possible
that on account of unfavorable topography and meteorological conditions, some
locations are more prone to particulate pollution. This needs to be carefully
considered while planning an industrial area or a residential township. The second

dimension to be considered here is the seasonal variation of particulates; in India,
summer season of the year (April to June) is associated with strong winds, low
humidity that can substantially reduce the level of ambient pollutants. In contrast, the
monsoon of the year (July to September) is associated with low wind speeds and
medium to heavy precipitation, which reduces the air pollution potential. The winter
(October to December) and spring (January to March) seasons of the year are
associated with low wind speeds and negligible rainfall resulting in buildup of
pollutants which increase the air pollution level of the studied location (Kavuri
and Paul 2013). Further, the lower solar insulation rates during the winter months
lead to lower atmospheric inversion layers where pollutants become trapped close to
the ground, further increasing fine particle concentrations (Gummeneni et al. 2011).
PM2.5 data confirms the pronounced seasonal peaks coinciding with lower mixing
heights of the winter months. It has been concluded that the measured PM pollution
in the winter is at least double the concentrations measured during the rest of the
season (Guttikunda 2009). Hence, in locations with topography and meteorological
conditions favoring atmospheric inversion layers, traffic load may be reduced by
odd-even car number plying on alternate days, industrial production on alternate
days, and other steps which can reduce public exposure to high PM concentration.
Another key point to be considered here is that mortality and morbidity effects
due to air pollution are not solely linked to ambient level concentration.
Human exposure to pollutants is affected by the amount of time spent outdoors
and by the amount of outdoor air that enters buildings and homes. So, reducing the
exposure is the key to reduce harmful effects of air pollution. Also, population
density affects the number of people exposed in a given area. Dose response to
pollutant exposure may vary for different people depending on their age, health
status, exposures to other stressors such as tobacco, and indoor air pollution
from cook stoves, and other factors. Therefore, study should be carried out
for various population subgroups with time spent in different environments and
the results should then be aggregated. Previous studies (Apte et al. 2011) have
highlighted a very important fact that the concentrations of air pollutants from
vehicles are elevated along roadways, indicating that human exposure in transpor-
tation microenvironments may not be adequately characterized by centrally located
monitors. Therefore, the actual pollutant levels to which public are exposed may be
several times greater than the concentration measured by the pollutant monitors.
Control Measures
In this regard, it is evident that PM pollution is a significant cause of mortality and

morbidity; Indian cities particularly the urban areas have a high PM concentration
making the population prone to its adverse effects. Therefore, it is urgent to under-
take suitable strategies for reducing it; particulate matter in ambient air could be
controlled by adopting the following measures:
1. Improvement of road conditions including repair of roads, widening of roads,

and construction of flyovers.
2. Vehicular emission check, compliance, and imposition of fine for
noncompliance.
3. Mass awareness campaigns to educate public about health effects of particulates.
4. Vehicles older than 15 years should be taken off from roads, strict implementa-
tion is the key.
5. Implementation of road cleaning (at least weekly) to check the resuspension of
road dust.
6. Encourage use of cleaner fuels like CNG in three and four wheelers and focus on
better mass transportation systems.
7. Industry needs to control its PM emissions and also ensure safety for its workers.
8. Better air monitoring systems in terms of accuracy and coverage a as well as the
data accessibility to the public would play an important role as a health advisory
system and increase the pressure on polluters to comply with regulatory
standards.
9. Planting trees (such as Azadirachtaindica, Ficusbengalensis, Mangiferaindica)
near roadsides which are known to be absorbers of particulate matter from
vehicles. Then they can be used effectively by planners and green belt devel-
opers in managing the urban air pollution (Mate and Deshmukh 2015).
10. Control of emissions from source is important but it is even more important to
reduce the exposure to particulates by wearing masks especially for those
exposed like traffic policemen and industrial workers.
11. Citing of residential townships and industrial zones based on the site meteorol-
ogy to reduce buildup of particulate load to which population is exposed.
12. Implementing odd even car days, rotation work days for industry to reduce the
particulate concentration particularly during the winter.
13. Highlighting air quality status especially during days classified as critical for
particulate pollution so that public is able to reduce exposure by wearing masks
and staying indoors.
Conclusion
In the last few decades, growing population, industrialization, and a tremendous

growth in vehicles have resulted in air pollution becoming a serious issue in
developing countries such as India. The situation is alarming as the population of
over a billion is exposed to harmful particulate matter which is associated with
severe form of health effects such as asthma, cardiovascular disorders, and even
cancers. This chapter critically examined the status of PM pollution in India, and it is
evident that majority of cities exceed the national standards for PM. Almost 85 cities
have been classified as critical with regard to PM 10 levels. Twenty-four states
and UTs have high PM concentrations way above the standards. In addition to
greater emission from pollutant sources, high PM loads may be due to site location
and meteorology, seasonal variation, etc. Therefore, careful planning of industrial
zone must be done to minimize exposure to residential areas. Proper monitoring of

PM levels and highlighting hot spots would also reduce public exposure to partic-
ulates. In addition better pollutant monitoring systems, public awareness regarding
the adverse effects of PM, efficient vehicle engines, use of cleaner fuels, etc. would
go a long way in mitigating the harmful effects of particulates.
Cross-References
Delhi City
▶ Management of Residues from Air Pollution Control Systems
Study of Delhi City
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Global Environmental Issues
8
Alsharifa Hind Mohammad
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
Water Issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
Sources of Fresh Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Water Scarcity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
Water Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
Air Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
Climate Change . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
Ozone Layer Depletion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
Acid Rain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
Abstract
Major Environmental Issues is a phrase that refers to the effects of human
activities towards the nature; these actions cause instability in the one or more
elements of the natural system. This chapter sheds the light on some of these
major issues to increase the human awareness about the environment. Water
issues come in the first rank as it is defined as a major factor for living thing;
water quality and quality taken into consideration during editing this chapter. Air
is another important element of any ecosystem; air pollution causes were pro-
duced in this part. Climate change; the newly issue faces the earth was selected to
be studied within this chapter because it is one if the major environmental issues
that id alarming nowadays and its effect is appearing clearly. Ozone layer and acid
rain are other two important issues that are studied because of their negative
effects on human and ecosystems in our nature.
A. H. Mohammad (*)
Water, Energy and Environment Center, The University of Jordan, Amman, Jordan
e-mail: hind_geology@yahoo.com

https://doi.org/10.1007/978-3-319-73645-7_127
196 A. H. Mohammad
Keywords
Water scarcity · Air pollution · Ozone layer · Acid rain
Introduction
Our Nature is currently facing many serious concerns that we cannot passing over
any more. As researchers, our role is to find solutions, either by adapting ourselves to
these serious problems or by mitigating their effects. The latter is best for the natural
system, but sometimes, because of environmental conditions, many decades are
needed to fix the problems that we have been creating for a long time now.
Water pollution is a major concern: clean drinking water is not commonly
available any more, and saline aquifers, polluted surface water bodies, overpumped
groundwater systems, and waste from industrial and agricultural activities pollute the
water humans, animals, and plants use> All these are major facts that are facing the
water supply all over the world.
Climate change and global warming are also very critical issues facing Mother
Earth. They are the result of human practices that increase greenhouse gas emissions,
leading temperatures to increase in the oceans and on the Earth’s surface, causing
polar ice caps to melt and sea levels to rise, and creating unnatural patterns of
precipitation such as flash floods, excessive snow, and desertification.
Depletion of the crucial Ozone layer of the atmosphere is attributed to pollution
caused by Chlorine and Bromide found in Chloro-floro carbons (CFC’s). The ozone
is an invisible layer of protection around the Earth that protects ecosystems from the
Sun’s harmful rays. Once these toxic gases (CFC’s) reach the upper atmosphere, they
cause depletion in the ozone concentrations which named as a hole. The CFC’s are
banned in many industries and consumer products.
One of the most important characteristics of the aforementioned and other
environmental hazards are that they affect all humankind on a global scale, without
regard to any particular country, region, or continent. The whole world is a stake-
holder, and this raises issues about who should do what to combat environmental
degradation. Thus, the issues listed above – and many others – are described in this
chapter.
Water Issues
Allah (s.w.t.) said in Quran, “We have made from water every living thing.”
Water resources are sources of water that are potentially useful for household,
agricultural, industrial, recreational, and environmental activities. Approximately
97% of the water on Earth is saltwater, which exists in oceans and seas, and only
3% is fresh water. Slightly over two thirds of that fresh water is frozen in glaciers and
polar ice caps (Earth’s water distribution 2009). The remaining unfrozen freshwater
is mainly groundwater, with only a small portion present above ground as surface
8 Global Environmental Issues 197
water (rivers and lakes) or in the atmosphere as clouds (Scientific Facts on Water:
State of the Resource 2008) (Fig. 1).
Fresh water can be divided into renewable and nonrenewable resources. A
renewable resource is that which could be recharged; that is, the consumed amounts
of the renewable water body will be replaced by another source such as rainfall. Both
ground and surface water bodies could be renewable if a source is available to
replace the amounts consumed. In the case of overdepletion of these sources, the risk
of them becoming nonrenewable water sources is high; this would be higher for
groundwater than for surface water resources. In fact, the world’s supply of ground-
water is steadily decreasing, prominently in Asia, the Middle East, North Africa,
South America, and North America, although it is still unclear how much natural
renewal balances this usage and whether ecosystems are threatened (Gleeson et al.
2012).
Sources of Fresh Water
Surface water – water in rivers, lakes, and wetlands – is the main source of fresh
water and is naturally replenished by rainfall and naturally lost through discharge to
oceans or through evaporation and evapotranspiration. Groundwater is replaced
through the natural water cycle. The water cycle describes how water changes
throughout the world in different physical forms: water evaporates from reservoirs
over the Earth’s surface, rises through the atmosphere, cools and condenses into
Surface/other Atmosphere Living things

Freshwater 2.5% 1.2% 3.0% 0.26%
freshwater
Rivers
0.49%
Other saline Ground-
water 0.9% water Swamps,
Lakes marshes
30.1% 20.9% 2.6%
Soil
moisture
Oceans Ground 3.8%
96.5% ice and
Glaciers permafrost
and 69.0%
ice caps
68.7%
Total global Freshwater Surface water and

water other freshwater
Fig. 1 Water resource distribution over the Earth (https://en.wikipedia.org/wiki/File:Earth%27s_

water_distribution.svg)
198 A. H. Mohammad
clouds, and falls again to the surface as precipitation (e.g., rain or snow). Water
falling on land runs over the surface to be collected in rivers and lakes, seeps into soil
and porous layers of rock, or flows into the oceans through floods, where it once
more evaporates. The cycling of water into and out of the atmosphere is a significant
aspect of weather patterns on Earth, and much of it flows back into the oceans.
The major environmental problems connected to water resources are water
shortage and water quality deterioration through pollution.
Water Scarcity
Water scarcity refers to the lack of available water resources sufficient to meet water
needs within a region. When “water needs” are mentioned here, it refers to all water
uses: household, agricultural, and industrial. Water scarcity affects every continent
and approximately 2.8 billion people worldwide at least 1 month of every year. More
than 1.2 billion people lack access to clean drinking water (Water Scarcity 2013)
(Fig. 2).
Another popular opinion is that the quantity of available rainwater is lowering
due to weather exchange. This decrease has decreased water flows within and river
flows, and has made lakes and ponds decrease. Many aquifers were over pumped
and aren’t recharging quick enough. Despite the fact that the overall fresh water
deliver isn't always used up, an awful lot has come to be polluted, salted, wrong, or
otherwise unavailable for drinking or for use in industry and agriculture. To keep
Little or no water scarcity Not estimated Approaching physical

water scarcity
Physical water scarcity Economic water scarcity
Source: International Water Management Institute
Fig. 2 Physical water scarcity and economic water scarcity by country

away from a global water disaster, farmers should attempt to growth productiveness
to meet developing demands for meals, while industries and towns discover methods
to apply water more efficaciously (Chartres and Varma 2010).
Water Pollution
Water is a colorless, tasteless, and odorless liquid. If any of these properties change,
then the water has been polluted. Pollution levels change according to the end use of
the water resource; quality restrictions are a must for drinking and household
purposes. If the water will be used to irrigate edible crops, then water quality must
also be very good.
Water pollution has become a global problem today, and water resource policy
must be evaluated continuously to counter this problem. Deaths and diseases
worldwide are caused by water pollution: approximately 14,000 people die every
day as a result (Letchinger 2000; Pink 2006; Larry 2006).
Both developed and developing countries face water pollution problems
depending on the pollutants produced by human activities and their behaviors
toward those pollutants (National Water Quality Inventory Report to Congress
2009). Many factors influence water quality, such as precipitation, climate, soil
type, vegetation, geology, groundwater, and human activities. Point sources of
industries and municipalities pose the greatest threat to water quality. Activities
such as mining, urban development, and agriculture also effect water quality.
Non–point source pollution also includes nutrients, sediments, and toxic contami-
nants (Florescu et al. 2010).
Different types of pollutants may have different properties. For example, stock
pollutants, which include nonbiodegradable plastics, synthetic chemicals, and heavy
metals, have no or very little absorptive capacity (Chaudhry and Malik 2017). These
pollutants accumulate in the environment over time, and with the increase of their
concentrations in nature, their effects increase harm to the system (Tietenberg 2006).
Air Pollution
“Air pollution” cannot be simply defined. One could claim that air pollution started
when humans began burning fuels. In other words, all man-made (anthropogenic)
emissions into the air can be called air pollution because they alter the chemical
composition of the natural atmosphere. The increase in global concentrations of green-
house gases – CO2, CH4, and N2O (shown in Table 1) – can be called air pollution using
this approach, even though their concentrations are not toxic to humans or the ecosys-
tem. One can refine this approach and consider only anthropogenic emissions of harmful
chemicals as air pollution (Daly and Zannetti 2007).
Air pollution occurs when harmful substances, including particulates and biological
molecules, are introduced into Earth’s atmosphere. Human activity and natural pro-
cesses can both generate air pollution.
200 A. H. Mohammad
Table 1 Atmospheric Chemical Compositions (Builtjes 2003)

Values in the Atmosphere
Current Atmosphere Natural Atmosphere Current Atmosphere
Gas Symbol (vol%) (ppm) (ppm)
Nitrogen N2 78.1
Oxygen O2 20.9
Argon Ar 0.92
Neon Ne 18.2
Helium He 5.2
Krypton Kr 1.14
Xenon Xe 0.09
Carbon CO2 280.0 370.03
dioxide
Methane CH4 0.750 1.774
Nitrous N2O 0.270 0.3185
oxide
Water H2O Variable (0.004–4)
vapor
Indoor air pollution and poor urban air quality are considered two of the world’s
worst toxic pollution problems, according to the 2008 Blacksmith Institute World’s
Worst Polluted Places report (Reports 2016). According to a 2014 World Health
Organization report, air pollution in 2012 caused the deaths of around 7 million
people worldwide (WHO 2014), an estimate roughly echoed by one from the
International Energy Agency (http://www.iea.org/publications/freepublications/pub
lication/WorldEnergyOutlookSpecialReport2016EnergyandAirPollution.pdf; Study
Links 6.5 Million Deaths Each Year to Air Pollution 2016). Figure 3 shows chart of
indoor and outdoor air pollution health risks.
Climate Change
Climate change is a global phenomenon and its impacts – changing rainfall patterns
and increasing global temperatures – are clearly obvious nowadays. Changes in
climate over years can be referenced to several factors, the most significant of which
is human activity in the form of global greenhouse gas (such as CO2) emissions.
Other gases such as nitrous oxide and methane are also harmful, but CO2 poses the
major threat to nature today. It is produced primarily from burning and consuming
fossil fuels. Figure 4 shows anthropogenic greenhouse gas emissions from IPCC
2014; CO2 is clearly the most significant emission (IPCC, Fourth Assessment Report
2007).
The meaning of “weather” must be distinguished from that of “climate.” Weather
describes the conditions of the atmosphere – temperature, pressure, humidity, wind,
and other key parameters (meteorological elements) – at a certain place and time.
Climate the composite or generally prevailing weather conditions of a region, as
7.0% 800,000
Disease burden due to indoor
air pollution as % of the total 700,000
6.0%
Disease burden due to outdoor
Percent of total health risks
DALYs per million people

air pollution as % of the total 600,000
5.0%
Total disease burden, DALYs
per million people 500,000
4.0%
400,000
3.0%
300,000
2.0%
200,000
1.0% 100,000
0.0% 0
India Sub- China Asia Middle- Latin Industrialized
Saharan and East and America countries
Africa Pacific North Africa
Fig. 3 Indoor and outdoor air pollution health risks(http://greenplanetethics.com/wordpress/

indoor-air-pollutiuon-facts-what-is-indoor-air-pollution-and-how-to-reduce-it/)
Fig. 4 Anthropogenic
greenhouse gas emissions
from 2004
202 A. H. Mohammad
temperature, air pressure, humidity, precipitation, sunshine, cloudiness, and winds,

throughout the year, averaged over a series of years. The relevant quantities are most
often surface variables such as temperature, precipitation, and wind. The classical
period for averaging these variables is 30 years, as defined by the World Meteoro-
logical Organization (Cubasch et al. 2013).
“Main drivers of climate change, as shown in Fig. 5, are the radiative balance
between incoming solar shortwave radiation (SWR) and outgoing long-wave radi-
ation (OLWR), both of which are influenced by global climate “drivers.” Natural
fluctuations in solar output can cause changes in energy balance. Human activity
changes gas and aerosol emissions, which are involved in atmospheric chemical
reactions that result in modified O3 and aerosol amounts. O3 and aerosol particles
absorb, scatter, and reflect SWR, changing the energy balance. Some aerosols act as
cloud condensation nuclei, modifying the properties of cloud droplets and possibly
affecting precipitation. Because cloud interactions with SWR and OLWR are large,
small changes in the properties of clouds have important implications for the
radiative budget. Anthropogenic changes in greenhouse gases (e.g., CO2, CH4,
N2O, O3, CFCs) and large aerosols modify the amount of OLWR by absorbing
OLWR and re-emitting less energy at a lower temperature. Surface albedo is changed
by changes in vegetation or land surface properties, snow or ice cover and ocean
color. These changes are driven by natural seasonal and diurnal changes, as well as
human influence such as changes in vegetation types) (Forster et al. 2007).”
Ozone Layer Depletion
Ozone is a gas which naturally produced in the upper atmosphere; it can be useful or
harmful for human health and the environment depending on its location. In the layer
near troposphere level; ozone recognized as bad ozone; it is a pollutant that produce
smog. But higher up, in the stratosphere; the good ozone exists to protect life on
Earth by absorbing some of the sun’s UV rays. An easy way to remember this is the
phrase “good up high, bad nearby” (https://www.epa.gov/sites/production/files/doc
uments/ozonedepletion.pdf) (Fig. 6).
The ozone layer is a layer literally; it is an area within the stratosphere that
contains the high concentrations of Ozone; this layer helps in absorbing most of the
harmful UV radiations from the sun. It contains high concentrations of ozone (O3) in
relation to other parts of the atmosphere, although the amount is small in relation to
other gases in the stratosphere. The ozone layer contains less than 10 ppm ozone,
whereas the average ozone concentration in Earth’s atmosphere as a whole is about
0.3 ppm. The ozone layer is mainly found in the lower portion of the stratosphere,
from approximately 20 to 30 km above Earth, although its thickness varies season-
ally and geographically (https://en.wikipedia.org/wiki/Ozone_layer). The ozone
layer has been defensive existence on planet Earth for billions of years; however
it’s now being worn out by way of human activities. humans commenced to value
the importance of the ozone layer while scientists released a studies finding
suggesting that certain human-made chemical compounds referred to as CFCs
8
Natural
Fluctuations in Ourgoing Longwave
SWR Reflected by Radiation (OLR)
Incoming
Solar Output the Atmosphere
Shortwave SWR
Radiation (SWR)
Global Environmental Issues
Chemical
SWR Absorbed by Aerosol/cloud Reactions
the Atmosphere Interactions
Clouds Ozone Greenhouse

Aerosols Gases and
SWR, LWR SWR, LWR
Large Aerosols
SWR LWR
Chemical
Reactions
Emission
of
Back Gases
Latent Longwave LWR
and Aeros
Heat Flux Emitte ols
Sensible Radiation d
(LWR) from
Heat Flux Surfa
ce
SWR Absorbed by
SWR Reflected by
the Surface
the Surface
Ice/Snow Cover
Vegetatio
Color n Chang
es
Ocean eight
H Surface
Wave
Albedo
Changes
SWR
203
Fig. 5 Main drivers of climate change. (Forster et al. 2007)

204 A. H. Mohammad
Fig. 6 Presence of good and the bad ozone within the stratosphere
controlled to reach the stratosphere and depleted the ozone via a profound series of
chemical reactions. The outcomes of this research look at caused the signing of a
international treaty known as the Montreal Protocol in 1973. This treaty helped to
lessen the production of these dangerous human-made chemicals (https://www.epa.
gov/websites/production/documents/documents/ozonedepletion.pdf).
CFCs were invented by Thomas Midgley in the 1920s. They were used in air
conditioning/cooling units, as aerosol spray propellants before the 1980s, and in
processes to clean delicate electronic equipment. They also occur as by-products of
some chemical processes. No significant natural sources have ever been identified
for these compounds – their presence in the atmosphere is due almost entirely to
human manufacture. When ozone-depleting chemicals reach the stratosphere, they
are dissociated by UV light to release chlorine atoms. The chlorine atoms act as a
catalyst, and each can break down tens of thousands of ozone molecules before
being removed from the stratosphere. Given the longevity of CFC molecules,
recovery times are measured in decades. It is calculated that a CFC molecule takes
an average of 15 years to go from the ground level to the upper atmosphere, and it
can stay there for about a century, destroying up to 100,000 ozone molecules during
that time. (Chlorofluorocarbons Information)
Acid Rain
Acid rain is rain that is more acidic than it should be. It is a complicated problem
affecting soil and water chemistry, as well as the life cycles of plants and animals on
land and in water. As mentioned before, the sulfuric acid is the most harmful
component in the acid rain; that leads to the fact of if we want to reduce this
phenomena we have to reduce the source of the problem by reducing the cause of
this problem (Fig. 7).
Acid rain causes acidification of fresh water bodies such as lakes and streams,
which affect negatively the ecosystems of those bodies. It also contributes to damage
of trees at high elevations and many sensitive forest soils. From an economical point
Fig. 7 pH values for acid rain and other liquids (https://www3.epa.gov/acidrain/education/

teachersguide.pdf)
of view, acid rain accelerates the decay of building materials and paints, including
irreplaceable buildings, statues, and sculptures that are part of a nation’s cultural
heritage. Before falling to Earth, SO2 and NOx gases and their particulate matter
derivatives, sulfates and nitrates, contribute to visibility degradation and harm
human health (http://nptel.ac.in/courses/104103020/4).
There are two main processes to produce acid depositions; namely; expelling the
hydrochloric acid directly into the atmosphere, this is the most common reason due
to the secondary pollutants that produced from the oxidation processes of the
nitrogen oxides (NOx) or SO2 gas. different reactions within the atmosphere can
convert those gases into sulfuric and nitric acids. this proceses usually take several
days and can be moved hundreds kilometers far away from the source of these
pollutants Fig. 8.
Emissions of sulfur dioxide are responsible for 60–70% of the acid deposited
globally. More than 90% of the sulfur in the atmosphere is of human origin. The
main sources of sulfur include:
• Coal burning: Coal typically contains 2–3% sulfur, so when it is burned SO2 is
liberated.
206 A. H. Mohammad
O3
SO2 H2SO4 2H+ + SO4−2

Oxidation
NOx HNO3 H+ + NO3−
NH3 + H+ = NH4+
Wet Deposition
Dry Deposition H+ NH4+ NO3− SO4−2
Emission Dry Deposition of Natural Wet Deposition of

Source Gases, Particles Ammonia Dissolved Acids
and Aerosols
Fig. 8 Dry and wet depositions of acid rain (http://nptel.ac.in/courses/104103020/4)
• Smelting of metal sulfide ores to obtain pure metals: Metals such as zinc, nickel,
and copper are all commonly obtained in this manner.
• Volcanic eruptions: Although this is not a widespread problem, a volcanic
eruption can add a lot of sulfur to the atmosphere in a region.
• Organic decay
• Ocean spray
SO2 + H2O »»» H2SO3

H2SO3 + 1/2O2 »»» H2SO4
The main sources of sulfuric acids include the burning of fossil fuel, volcanic
eruptions and ocean sprays, after being released to the atmosphere the sulfur oxide
could be deposited to the earth through a dry form or will go through wet reactions
to produce the sulfuric acids through the up mentioned equations.
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WHO (2014) 7 million premature deaths annually linked to air pollution. Retrieved 25 Mar 2014
Water scarcity. International decade for action ‘Water for life’ 2005–2015. un.org. Retrieved 20 Oct
2013
Fluoride Contamination in Groundwater
and the Source Mineral Releasing Fluoride 9
in Groundwater of Indo-Gangetic Alluvium,
India
Abhishek Saxena
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
Geomorphology of Indo-Gangetic Alluvium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
Fluoride in Groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
Monthly Variation of Fluoride with Depth- . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
Sedimentological and Mineralogical Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
Mineralogical Composition of Sand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
Correlation Between the Fluoride Content in the Water and Vertical Variation in the
Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
Mineralogical Composition of Mud . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
Mineralogical Composition of Silt Fraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
Mineralogical Composition of the Clay Fraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
Illite and Mica Minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
Smectites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
Chlorite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
Kaolinite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
Geochemistry of Sediments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
Major Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
Trace Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
Interelement Relationship Between Major Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
Interelement Relationship Between Trace Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
Interelemental Relationship Between Major and Trace Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
Chemical Maturity of the Sediments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
A-CN-K Diagram and Chemical Index of Alteration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
Relative Mobility of the Elements with Respect to Al2O3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Elemental Ratio for Major Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Chemical Mobility of Elements with Respect to Weathering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
Distribution of Major Elements with Depth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
A. Saxena (*)
Faculty of Civil Engineering, Sri Ramswaroop Memorial University, Barabanki, Uttar Pradesh,
India
e-mail: abhishek.ce@srmu.ac.in

https://doi.org/10.1007/978-3-319-73645-7_128
210 A. Saxena
Weathering and Release of Fluoride in Groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
Abstract
The problem of high fluoride contaminated groundwater is one of the major
drinking water issues of the world. This problem is not only affecting the under
developed/developing nations but also adversely impacting the most developed
nations. Drinking fluoride contaminated water leads to a very painful disease
called fluorosis, which is noncurable and may be fatal in later stage. Although
minor values of fluoride in our food intake is necessary for the dental health, if it
is consumed beyond the permissible limit then it may cause serious damage to our
teeth, muscles, and bones. The fluoride content in groundwater is generally
related with hard rock terrains but in last few decades it had been widely reported
from the alluvial plains. The Indo-Gangetic Alluvium, which is one of the largest
alluvial plains of the world, is also severely affected by this issue. Thus, a detailed
study was done in this area to decipher the reasons for the release of fluoride into
the ground water as there is no hard rocks reported in the nearby areas, and it was
suspected that this fluoride is leaching from sandy or clayey soils. The study
includes the mineralogical identification of various minerals found in the sedi-
ments. The probable mineral releasing the fluoride in the groundwater of the
affected area was identified from the sand fraction. Interestingly, the Chemical
Index of Alteration (CIA values) analyzed for the sediment samples confirmed the
various rate of weathering active in the area, and the minerals were in the various
phases of alteration. One such mineral was identified as biotite which was under
the process of alteration into chlorite and was the main reason for releasing the
fluoride into the ground water.
Keywords
Fluoride contamination · Groundwater · Source mineral · Chemical index of
alteration · Painful disease
Introduction
In recent times, high fluoride pollution in drinking water and its health impact has
become one of the most highlighted problems of the twenty-first century. Small
amount of fluoride (less than 1 ppm for India, WHO 2004) is very essential for the
formation of dental enamel, normal mineralization of bones, and curing dental
caries. But high intake of it is a very serious matter of concern for our health as it
may cause dental fluorosis, muscular fluorosis, and/or skeletal fluorosis, which may
even prove fatal. The fluorosis has not only adversely affected the third world but
also a serious matter of concern for the most developed nations. The occurrence of
fluoride in drinking water is reported from many parts of the developed countries. In
9 Fluoride Contamination in Groundwater and the Source Mineral. . . 211
countries like UK, USA, and Mexico, this problem is alarming and is emerging and
effecting large section of population due to high consumption of fluoride and
unawareness regarding the adverse effect of this element. This is because they are
still following the old concept of drinking fluorinated water and using fluorinated
toothpastes. At present, 99% of western continental Europe has rejected, banned, or
stopped fluoridation due to environmental, health, legal, or ethical concerns. Many
fluorosis patients belong to rural, tribal, or other backward areas of these countries.
Factors such as hard labor under the open sun, higher drinking water consumption,
and dietary malnutrition result in fluoride toxicity. The problem of fluorosis had also
being related to the socioeconomic condition of the people as the fluorosis endemic
areas are either underdeveloped or developing nations. The cases of dental fluorosis
in many school children in the northern part of Sri Lanka were reported in as early as
1974. The rural water supply and sanitation projects by tubewells had enhanced the
fluoride problem in this island. The similar problem is being faced by many other
countries where the poor rural people are most adversely affected. In India, fluorosis
was first detected by farmers of Andhra Pradesh (Nellore district) when they found
that their cattles used for ploughing purposes had become weak within a period of
6 months of buying and thus become inefficient for any work. Since then there are
about half a million of people in India reportedly suffering from ailments due to
excessive fluoride in drinking water (Fig. 1).
The Indo-Gangetic Alluvium is the largest Quaternary alluvial plain of the world.
It is extensive alluvial plain of Ganga, Indus, and Brahamputra Rivers and their
tributaries, which separate the Himalayan ranges from Peninsular India. It is highly
COUNTRIES WITH ENDEMIC FLUOROSIS DUE TO EXCESS

FLUORIDE IN DRINKING WATER
Iraq
Turkey
Syria
Jordan
Palestine
Morocco
Japan
Algeria
China
Libya
Bangladesh
Egypt
Iran Thailand
Mexico Senegal India
Pakistan
Ethiopia
Uganda Sri Lanka
United Arab Kenya
Emirates
Tanzania
Australia
Argentina
New Zealand
Fig. 1 Status of fluoride in the different parts of world (After Susheela 2003)
212 A. Saxena
fertile and thickly populated plain, which hosts one-third of India’s population and
produces two-thirds of the country’s rice and wheat. The plain experiences a wide
range of climate (from arid to humid), landscape (dune to flat plain), soil (Regosols
to Vertosols), and social structure (nomadic habitat to metropolitan cities)
(Saini et al. 2001). It is mainly composed of sand, clay, and silt, which must have
been brought up by the rivers from both the Himalayas and peninsular India. In the
last few decades, it has been noticed that in many parts of Unnao district the people
and cattles living in this densely populated area are suffering from a very painful
disease known as “fluorosis.” It is an incurable disease which is caused due to
excessive intake of fluoride generally through drinking water. Uttar Pradesh is the
most populated state of India. The state is agriculture dominant and about 70% of its
population live in rural areas. The first published report on fluorosis in Uttar Pradesh
was way back in 1937. The disease was then known in four states of India viz.,
Andhra Pradesh, Tamil Nadu, Punjab, and Uttar Pradesh. Since then the disease is
being reported in 20 states out of 35 states and union territories. The probable reason
for the spread of the disease is as follows:
1. Population over growth, necessitating for more and more water

2. Indiscriminate digging of tubewells
3. Unawareness about the drinking water quality
4. Poor diet and malnutrition in rural areas
Geomorphology of Indo-Gangetic Alluvium
Ganga plain is an active foreland basin formed as a result of continent-continent

collision of the Indian plate with the Asian plate. The rivers originating from the
Himalaya deposit their load in the alluvial plain, which forms the world’s largest
alluvial tract known as “Indo-Gangetic Alluvial tract” (Ansari 1997).
The Ganga plain in UP is classified into four hydrological units, viz. Bhabar, Terai,
Central Ganga Plain, and Marginal Alluvial Plain (Pathak 1982 in Khanna 1992). The
alluvial sediments of Ganga basin have been classified as Older Alluvium and Newer
Alluvium. The former consists of sediments which were formed in distant past and are
partly undergoing denudation, while the latter is under its process of formation. The
Older Alluvium is made up of massive beds of clay of a pale reddish brown color, very
often yellowish with Kanker present in between the clay layers. The Newer Alluvium
is light colored and poor in calcareous matter. The major part of the Central Ganga
Plain is composed of Older Alluvium (Khanna 1992).
The Gangetic Plain is a flat alluvial tract. The soil exhibits a wide variance; sandy
on the elevated locations, clayey in the topographical lows, and loamy on the flat
surfaces. The area is mud (silt + clay) dominated and thus leads to water logged
conditions (Fig. 2a, b), which is supposed to be responsible for the sodic soil present
in most of the areas (Fig. 3a, b).
As the representative area of the Indo-Gangetic plain, Unnao district had been
selected for the detailed study for fluoride pollution. The Nawabganj Block (area) of
Fig. 2 Waterlogged area in the (a) eastern and (b) southern side of Marksnagar Village, Nawabganj
Block
Fig. 3 (a) The view of the sodic soil of the study area; (b) close-up view of the sodic soil with
abundance of white encrustation of salts
Unnao district (an administrative division), Uttar Pradesh, and is the central part of
this Gangetic alluvial plain. The Ganga and Sai are the main rivers of the area and are
responsible for the many paleo-channels and ox-bow lakes in the area. The general
trend of both the rivers is north–west to south–east. According to Singh (1992),
this alluvial plain has a gentle consistent regional slope and a narrow range of grain
sizes but the channel shows a variety of forms namely braided, slightly sinuous,
highly sinuous, anastomosing, ox-bow lakes, etc. (see Fig. 4).
Sharma et al. (2004) using remote sensing data described that the saline-sodic
soils are the dominant salt-affected soils in Indo-Gangetic plain. There are very small
patches of saline soils along the flood plains. These soils have salt encrustation of
white to dull white tone as seen in satellite data FCC print. The saline soils have
predominantly chlorides and sulfates of Na, Ca, and Mg. These are the soils with
neutral soluble salts have saturation paste pH <8.5. While the soils containing
excess of salts capable of alkaline hydrolysis such as sodium carbonate, sodium
bicarbonate, and sodium silicate have the pH of saturated paste >8.5. In saline salts,
the predominant salts are chlorides and sulfates of Ca and Mg. When there is a
relative predominance of Na then such soils have been termed as saline-sodic.
214 A. Saxena
Fig. 4 Types of river channel found in the study area (After Singh 1992) (A braided, B sinuous, C
meandering, D small sinuous, E complex sinuous, F highly sinuous tortuous, G narrow sinuous, H
abandoned sinuous)
The problem of soil salinity and water logging in the area has posed an extensive
threat to the geoenvironment of the area by increasing salt content in its upper surface,
moistening the soil, and decreasing the oxygen availability in the root zone. The silt-
clay surfaces in the paleo-channel zones, the channel command areas, bluff zones of
lowland, and the depressions are the most susceptible to these hazards where capillary
rise of groundwater under semiarid condition lead to the enrichment of salts and
modify the land into wasteland (Saini et al. 2001). This also leads to a very low
groundwater recharge, which results in degradation of groundwater quality (Fig. 5).
The Ganga plain foreland basin is divided into three subdivisions:
(a) Peidmount plain: Located adjacent to the Himalayan mountain belt, where the
sediment fill is in direct response to the thrust-fold tectonics, flexed lithosphere,
and subsidence.
(b) Central alluvial plain: It shows most of the south and southwest flowing
drainage swinging, in general, to southeast and east direction. All the major
river from Himalayas follow this trend and their southern bank shows Piedmont
cliff and escarpments.
(c) Marginal alluvial plain: It forms the southernmost part of the Ganga plain and is
characterized by restricted thickness of alluvium over the basement; hence the control
of structural features of the basement on the drainage network is quite common.
Fig. 5 Geological setting of the study area (depicted by letter “A”) (After Singh 1992)
The study area is the part of Central Alluvial plain where the general trend of
Ganga river is NW-SE, which is also the tectonic lineament direction of Central
Alluvial plain (Fig. 6).
Geophysical studies done by CGWB in 1992 using Electric logs, four groups of
aquifers namely 1, 2, 3, and 4 are recognized in order of increasing depth. Group
1 aquifers extend from water table to depth of 50–110 m underlined by Group
2 aquifers in depth of 70–260 m, followed by Group 3 aquifers in depth of
90–375 m. The Group 4 aquifers show upper boundary in depth of 280–400 m,
while the lower limit remains largely unexplored (Fig. 7).
According to Chaturvedi et al. (1992), the Group II aquifers contains groundwater of
deteriorated quality (resistivity less than 5 ohms) while that of Group I, III, and IV
contain good quality of water. The groundwater in the area occurs under unconfined and
confined conditions. The shallow aquifers that range upto 110 m bgl have number of
phreatic aquifers. The aquifers material is fine to medium grained sand and generally
micaceous in nature with Kankar. The chemical analysis of groundwater (Rai 1997) of
Unnao district indicates that both good and moderate/bad quality groundwater are found
in the sand-dominated areas and moderate and bad quality groundwater occur in clay-
dominated areas under confined and semi-confined conditions. The bad quality of water
is mostly found in waterlogged areas and shows an increasing trend of groundwater
salinity/alkanity. The problem of leaching of fluoride in groundwater is more confined to
this zone and had affected the local population adversely. The high fluoride content is
found in well water which intersects clay-dominating sediments, and water level is in
shallow/critical conditions due to excess recharge from canals. Since there are sodic soils
the groundwater contaminated with high fluoride is also alkaline with high sodium
bicarbonate and sulfates. Thus, the fluoride in groundwater of Unnao district is closely
related with soil/groundwater alkalinity under waterlogged conditions.
216 A. Saxena
Fig. 6 General lithology of the Central Indo-Gangetic plain (After Hakim et al. 2001)
Fluoride in Groundwater
On the basis of available literature, a reconnaissance survey was conducted in the

Unnao district and the village Marksnagar of Nawabganj Block was identified as the
most adversely affected village due to high content of fluoride in the dugwell inside
the village. Most of the villagers use the water of this dugwell for drinking purposes.
The depth of this dugwell was found to be 5 m from the ground surface.
Apart from this, it was also found that the nearby villages are also having higher
concentration of fluoride in the water of their dugwells and handpumps as seen in
Jarwakhera, Aimakhera, Chaida, etc. However, the water of these villages show less
fluoride in comparison to the dugwell inside Marksnagar village. Four piezometers
were installed in Marksnagar itself at various depths for the regular monitoring of
water from different zones of aquifer. The water samples from these sites were
collected for the period of 2 years, i.e., from Feb 2002 to Jan 2004. Since
Marksnagar lies in the microlow area, a catchment area of 2.85 km2 around the
village was demarcated; outside this catchment area, the sampling for premonsoon
and postmonsoon period for the year 2003 was done to gain more information about
the spatial variation of fluoride around the Marksnagar village. Around 37 sampling
Fig. 7 Group of 4 aquifers reported by CGWB (1992)
sites were selected for the analysis of fluoride, pH, Ec, and bgl for the premonsoon
and postmonsoon period of 2003. The water sampling was done in the first week of
each month. The monthly data is subdivided into premonsoon (average of the
analytical data for the months of February, March, April, and May), monsoon
(average of the analytical data for the months of June, July, August, and September),
and postmonsoon period (average of the analytical data for the months of October,
November, December, and January) for evaluation (Fig. 8).
It is concluded from the analysis that for the year 2002 the average higher content
of fluoride in the water was during the premonsoon period while the monsoon period
gave lower values. But the reverse finding was noted for 2003, where the average
higher content of fluoride in the water was during the monsoon period while the
premonsoon period gave lowest values. This may be possible due to the different
amount of rainfall in both the years as well as due to the commencement of late
monsoons in 2002. In 2002, there were drought-like conditions due to less rainfall in
the area, while in 2003 there was normal monsoon. The rain water increases the ionic
strength of the ground water (Deshkar 1998), which promotes the high release of
fluoride in the water. Thus, in 2003, high values of fluoride are noted in the monsoon
period. However, the values for Mark II handpumps and for the dugwell adjacent to
the canal were found to be well within the recommended value for drinking purposes.
218 A. Saxena
INDIA
80°30’04”E
BITHUR
UNNAO
26°41’42”N KANPUR
G
AN
G
A
R
IV
Marksnagar
ER
Durgajkhera
Nawabganj
Block
Asoha
Village Block
City
26°27’59”N
0 3Km 80°56’31”E
Fig. 8 Location map of the study area (After Kumar and Saxena 2011)
Monthly Variation of Fluoride with Depth-
If the monthly variation of fluoride in the ground water for 2 years is considered then,
a general trend in variation in the concentration of fluoride in ground water was
found. This trend in variation could be broadly divided into five zones at different
depth intervals. They are viz.:
1. Zone I: Depth range of water table lying above 10 m below ground level. It
includes the water from dug wells and piezometers installed at depth less than
10 m (No. of samples monitored = 3).
2. Zone II: Ranging in depth interval of 10–20 m below ground level and includes
piezometers installed in this zone (No. of samples monitored = 4).
3. Zone III: Ranging in depth interval of 20–30 m and includes two Marks-II
handpumps (No. of samples monitored = 2).
4. Zone IV: Ranging in depth interval of 30–40 m and includes piezometers
installed in this zone (No. of samples monitored = 3).
5. Zone V: Ranging in depth interval of 40–45 m. Only one piezometer installed at
42 m and labeled as NP-4 was monitored at this zone (No. of samples
monitored = 1).
The monthly variation of fluoride in groundwater in all the five depth zones was
plotted together (see Fig. 9), and a few similarities in all these depth zones were
Monthly variation of fluoride at different depth zones

9
8
7
Fluoride(ppm)
6
5
4
3
2
1
0
Feb'02
Mar'02
Feb'03
Mar'03
June'02
June'03
May'02
May'03
Jan' 04
Jan'03
Dec' 03
July'02
Sep'02
Nov'02
Dec'02
July'03
Sep'03
Nov'03
Oct'02
Oct'03
Aug'02
Aug'03
Apr'02
Apr'03
Months
Zone I Zone II ZoneIII Zone IV Zone V
Fig. 9 Monthly variation of fluoride at different depth zones
noted. The fluoride concentration in all the depth zones increases in the month of
January for both the years, i.e., for 2002 and 2003. Besides this there is an increase of
fluoride in all these zones for the months of April, August, and October of the year
2002 and May, July, and September of the year 2003. A general decrease in the
fluoride content was noted in all the depth zones for the months of March, June, July,
September, and November of 2002 while in the year 2003 this decrease was seen in
the months of February, April, June, August, October, and December. But there is an
exceptional case for Zone I in which fluoride content did not decrease rather showed
an increase in the value for the month of June for 2002 and 2003. Broadly, it can be
inferred that June is a common month for both 2002 and 2003 in which a general
trend in the decrease of fluoride content was noted.
A cumulative graph was plotted for all the five zones along with the average
variation in water table depth (Fig. 10) to see any pattern in the variation of fluoride
and with the changing water table depth. The monthly mean of fluoride is depicted
by a line while the monthly mean of water table below ground level (bgl) is
represented by bars for all the sites. It is inferred that fluoride in the ground water
can be released with the fluctuation in the water table depth, but no definite positive
or negative correlation could be established between the two. However, generally
there is some release of fluoride with the relative decrease in the water table depth as
it is seen for the month of August 2002 as the water table depth for this month is
shallower than July 2002 and again for the month of October 2002 when the water
table depth is shallower than September and November 2002. The similar situation
was also seen for the month of January 2003, when the average water table depth
was shallower than the months of December 2002 and February 2003. Exception-
ally, though in the month of October 2003, the water table was lowest and was
220 A. Saxena
6
5
4
Fluoride(ppm)
3
2
0
Feb'02
Mar'02
Feb'03
Mar'03
Jan'03
May'02
May'03
Jan' 04
July'02
Sep'02
July'03
Sep'03
Nov'03
June'02
Nov'02
Dec'02
June'03
Dec' 03
Oct'02
Oct'03
Aug'02
Aug'03
Apr'02
Apr'03
-1
bgl (m)
-2
-3
-4
bgl Fluoride
Fig. 10 Monthly variation of fluoride with the fluctuation in the water table depth
around 1.5 m from the ground surface but very low fluoride content was detected in
the water, while fluoride content was remarkably higher for the months of September
and November 2003 when the bgl was around 2.0 m. This suggests that with the
relative decline in the water table there is always a possibility of the release of
fluoride in the water.
A definite relationship exists between the fluoride and the depth of water table
(bgl). It was found that usually as the water table rises up due to recharging from the
canal water and/or from the rain water then there is a definite decrease in fluoride
because of the dilution of the high fluoride water with low or no fluorinated water as is
the case seen in Nawai, Rahamatganj, and Durgajkhera. But an exceptional case was
noted in Marksnagar where the water table becomes shallower due to recharging but
the fluoride concentration increases. A possible explanation can be that as the water
level is increased then at optimum pH the fluoride already adsorbed in the clay is
released in to the water making it enriched in fluoride. Moreover, as the rain water
increases, the ionic strength of the ground water also ultimately facilitates the release
of fluoride. If the fluoride is plotted with depth then two zones are identified: one zone
with low concentration (i.e., concentration of fluoride <1.0 ppm) and another with
high concentration of fluoride (>1.0 ppm) in its water. The graph was plotted on the
basis of data of 15 regularly monitored sites for the period of 2 years. The fluoride is
represented on the x-axis while depth is represented on y-axis (see Fig. 11).
Fig. 11 Distribution of surface water

fluoride at various interval of
Depth (bgl in meters)

depth 0-10m
10-20m
20-30m
30-40m
40-45m
0 1 2 3 4 5
Fluoride (ppm)
2003-04 2002-03
Fig. 12 Variation of fluoride

surface water
with depth
0-10m
Depth (bgl in meters)
10-20m
20-30m
30-40m
40-45m
0 1 2 3 4 5
Fluoride (ppm)
2003-04 2002-03 2003-04(e)
It can be visualized from the graph of both the years that there is a general trend of
no or very low fluoride in surface water and then there is a remarkable increase up to
the depth of 20 m. The average concentration of fluoride again decreases between the
depth interval of 20 and 30 m and reaches to the 1 ppm level or even less suggesting
that water of this zone is comparatively safer for drinking purposes. Then again the
average concentration of fluoride increases below the depth interval around 30–40 m
and even reaches to 3.33 ppm between the depth interval of 40–45 m. To confirm
these findings, data of all the 37 sites was incorporated. Though these sites consist of
12 dugwells normally less than 6 m deep and 12 handpumps that are usually installed
between 15 and 25 m of depth, the piezometers installed below the depth of 25 m
were only the source for the data deeper than 25 m. Figure 12 gives the variation of
fluoride content in the water along with the depth. It can be clearly interpreted from
this figure that the surface water and the ground water of the depth zone of 20–30 m
are comparatively unpolluted and are safer and thus could be used as potable water
so the fluoride intake by the villagers residing in these area could be reduced.
222 A. Saxena
Sedimentological and Mineralogical Studies
The main objectives of the present study were to decipher the natural source of
fluoride in the study area and to understand the physicochemical environment that
leads to the leaching of fluoride into the groundwater. Attempts were also made to
identify the depth zones which are responsible for the release of fluoride into the
shallow aquifers. This necessitated the sedimentological and mineralogical study of
the sediments up to the maximum depth to which the piezometers have been
installed. It is also suspected that the clay minerals might be the source of fluoride
in the groundwater of the study area so the main focus was on the identification and
characterization of clay minerals by using X-Ray powder Diffraction (XRD)
method.
Grain size analysis was done for 20 sediment samples collected during the
installation of piezometer NP4 and NP10. The 15 samples were of Marksnagar
while only five representative samples of Durgajkhera were taken for the grain size
analysis. In Marksnagar, it was found that the sediments are mud dominant and
contains 76% of mud by weight while sand fraction was found to be only 11% and
rest 13% was made up of kanker. The general lithology at Durgajkhera is sand
dominant with 52% of sand. The mud fraction at Durgajkhera is made up of only
48%. Kanker at Durgajkhera are present below the depth of 18 m, though a few
patches of fine kanker are found above this depth.
Mineralogical Composition of Sand
The minerals of the sediments of Marksnagar were identified under the microscope,
and an attempt was made to identify the vertical variation in the mineralogy of
Marksnagar with depth. Mineralogy of the sand fraction of Durgajkhera was also
done. Muscovite, biotite, quartz, and feldspar are the dominant minerals at
Marksnagar and Durgajkhera. The percentage of quartz was the maximum at
Durgajkhera. The minerals at Marksnagar are comparatively more altered than
Durgajkhera and are generally more micaceous in nature. In total, about 350 grains
were counted for the each slide and the vertical variation in the grain count
percentage of the sediments of Marksnagar is given in Table 1.
Among all the minerals present in the Marksnagar, feldspar and biotite were
found to be altered. Plagioclase and microcline were the main types of feldspar
identified but were present in highly altered form. The variation in the mineralogy
along with the depth was found as it can be seen in the Table 1. In Durgajkhera as
described earlier, the dominant sediment fraction is made up of sand. The mineral-
ogical studies of the sand samples of Durgajkhera gave a higher content of quartz
and feldspar over the biotite and muscovite. Above that the mineral grains were
found to be less altered than that of Marksnagar. The sand can be grouped under
quartz (feldspar) arenite.
9
Table 1 Grain count percentage of the dominant minerals present in the +120 size fraction of Marksnagar
Depth Total Total
S. (bgl in Biotite Muscovite [Bio + Musc] Quartz Feldspar Qtz + Felds Rock Fragment Accessary Minerals
No m) (%) (%) (%) (%) (%) (%) (%) (%)
M1 0–3 32 15 47 23.8 17.3 41.1 8.7 <1
M2 3–6 16.9 3.1 20 23.1 35.4 59 3.7 4.6
M3 6–9 26 18.6 44.6 25.4 24.3 50 5.6 8.12
M4 9–12 21.7 11.6 33.3 24.64 29 54 4.35 <1
M5 12–15 28.4 22.4 50.8 18 26 44 3.3 4.2
M6 15–18 24 13.7 37.7 16 39.6 55.6 1.3 <1
M8 21–24 15 16.7 31.7 37.68 26.1 64 3 2.4
M9 24–27 27.5 18 45.5 16.2 34.3 51 1.2 <1
M10 27–30 13.8 18.2 32 16.7 36.7 53.4 16.96 1.16
M11 30–33 19 25.7 44.7 30.6 19.75 51 3.5 <1
M12 33–36 20.4 16.03 36.4 23.3 35 58.3 4.4 <1
M13 36–39 25.6 26.9 52.5 25.8 14.1 39.9 5.6 <1
Fluoride Contamination in Groundwater and the Source Mineral. . .
M14 39–42 24.9 19 43.9 25.6 24.75 51 2.5 1.0.5

M15 42–45 28.9 23.6 52.5 17.6 22.1 39.7 5.6 <1
223
224 A. Saxena
Correlation Between the Fluoride Content in the Water

and Vertical Variation in the Mineralogy
Some relation between the fluoride content in the ground water and the vertical
variation in the mineralogy of the Marksnagar exists. It was found that the high
content of fluoride in the ground water coincides with the high content of micaceous
minerals in the sediments. When the concentration of quartz and feldspar is higher
than that of muscovite and biotite then the concentration of fluoride in the ground
water is lower. Thus it can be said that the fluoride releases in the ground water
probably due to the alteration of micaceous mineral specially biotite. The biotite
present in the sediments was found to be altered. The presence of chlorite in the
sediments may be due to the alteration of biotite.
Mineralogical Composition of Mud
In total 20 bulk sediment samples of the mud were analyzed for Marksnagar and
Durgajkhera. Fifteen samples were of Marksnagar while five samples were of
Durgajkhera that were analyzed with the help of XRD.
The minerals identified in the bulk mud samples of Marksnagar are quartz
(at 3.32 Å), mica (muscovite and illite at 9.8–10 Å), plagioclase feldspar (probably
albite at 3.18), and alkali feldspar (probably microcline at 3.22 Å). A small peak of
kaolinite group (probably amesite at 6.9 Å) in and after the sediment samples at the
depth of 12–15 m was also found. Chamosite (at 4.7 Å) of chlorite group was also
identified in the sediment samples at the depth of 18–21 m and 21–24 m (Fig. 13).
Mineralogical Composition of Silt Fraction
The silt fraction of the representative sediment samples was separated from the bulk
samples of mud. Two of the representative samples of the Marksnagar were studied
under the XRD for their mineral identification. The silt fraction of all these samples
was found to be similar to that of the mud fraction. The peak of quartz was found to
be very prominent see Fig. 14.
In the silt fraction of Marksnagar, a peak of quartz was found at 3.3346 Å and
another at 4.2 Å. Among the feldspar, albite and microcline were identified at the D
spacing of 3.13 Å and 3.18 Å, respectively. A peak of muscovite-2 M2, calcian at
9.98 Å was also identified though its another peak at 3.3303 could not be identified
due to its overlapping with the peak of quartz.
Mineralogical Composition of the Clay Fraction
As described earlier that 0–8% of the clay by weight was found in the sediment
samples of Marksnagar while in Durgajkhera it was present even below 2%. So, clay
qtz.
(9-12m)
ill/musc.
qtz. mic.
alb.
(12-15m)
(15-18m)
(18-21m)
(21-24m)
mont. ame. qtz.

musc.
cham. alb.
0 5 10 15 20 25 30 35
TWO THETA (IN DEGREE)
Fig. 13 Mineral composition of bulk sediments at Marksnagar

226 A. Saxena
Fig. 14 Mineralogy of the

silt fraction of Marksnagar
samples of Marksnagar were only analyzed for the XRD mineral identification. The
clay mineral identification was done for the sediment samples of 6–9 m, 30–33 m,
and 33–36 m as some significant amount of clay was found at these depth zones. The
clay minerals identified broadly belongs to the mica, smectite, chlorite, and kaolinite
groups with the peak of mica group to be the most strong.
Illite and Mica Minerals
Illite shows a strong basal peak approximately at 8.9 2θ 10 Å, with a series of other
peaks at 4.96 Å and at 3.4 Å. These peaks remain unaffected on heating and
glyconation, though on heating a more intense peak was found. A peak at 9.8 Å
was also found and it was identified as muscovite. On glyconation, this peak remains
unaffected but it is absent on heating. The other peaks of muscovite were found at
4.99 Å and 3.33 Å. (Since it is very difficult to differentiate between the illite and
muscovite so both these minerals are put in one category and named as illite-mica).
Smectites
A basal peak of sauconite at 16.8 Å was identified which broadens marginally to

17.2 Å on glyconation though smaller peaks of sauconite are also found at 15.6 Å,
7.9 Å, and 8.2 Å. On heating, all the peaks of sauconite collapsed. The montmoril-
lonite gave its significant peaks at 13.4 Å, 12.8 Å and at 10.5 Å. In dehydrated
samples, all these peaks are collapsed except for that at 10.5 Å, which is reduced to
10.4 Å. The peaks of montmorillonite expands from 10.5 Å to 14 Å up on glycolation.
All the major peaks of smectites were found below an angle of 10 and which gets
collapsed on heating confirms the presence of smectite group. The peaks present at the
angle of 7.3 and 7.8 with the d-spacing of 12 Å and 11.2 Å could not be identified
precisely. These peaks may be of some intermediate stage between the monmorillonite
and illite. Among the various species of smectites, montmorillonite of the dioctahedral
subgroup and sauconite of the trioctahedral subgroup of smectite were identified.
Chlorite
Chlorite shows a peak at 14.2 Å followed by a peak at 7 Å, 4.7 Å, 4.2 Å, and 3.5 Å.
On dehydration by heating at 550 C, the presence of chlorite was confirmed as
indicated by the increase in the intensity of the peaks. The probably identified
minerals of this group are of trioctahedral subgroup and are chlinochlore (at 4.7 Å)
and vermiculite (at 14.14 Å followed by a peak at 4.75 Å and 4.2 Å). The vermiculite
can be differentiated from the other minerals of this group on its special response to
the dehydration and glyconation. On glyconation, the peak of vermiculite at 14.14 Å
shifts to 15 Å, and this is a characteristic feature of vermuculite. Furthermore, on
heating at 550 C almost all the peaks of vermiculite collapsed.
Kaolinite
Identification of kaolinite in the presence of chlorite was bit difficult as its basal peak
was found at 7.1 Å while that of chlorite is at 7 Å. However, a peak of kaolinite was
identified at 7.1 Å followed by a peak at 3.2 Å. On heating at 550 C, the strong peak
of kaolinite at 7.1 Å gets reduced and even get collapsed, confirming the presence
kaolinite. On glyconation, this peak remains unaffected and is found to be in the
range of 7.07–7.1 Å. Another mineral, amesite of this group was also identified in
the bulk sediments of mud. The presence of kaolinite indicates the feldspar
weathering (Ollier 1969).
Geochemistry of Sediments
The present section deals with the geochemistry of the sediment samples collected
from Marksnagar and Durgajkhera during the installation of piezometers in 2002 and
recent point bar deposit of Ganga river at Kanpur and Bithur in the year 2004. The
basic aim of this was to study the sediment characteristic and the weathering control
in the mobility of the elements. The sediments of Marksnagar and Durgajkhera were
selected for the detailed study as the maximum value of fluoride was found in the
ground water of Marksnagar while the ground water of Durgajkhera is compara-
tively less contaminated. The chemical analysis of sediments was done by X-Ray
Fluorescence Spectrometry (XRF) at the laboratory of The Chair of Applied
Geology; Institute of Geology and Mineralogy, University of Erlangen- Nurenberg,
228 A. Saxena
D- 91054 Erlangen, Germany. Philips PW 2400 X-Ray fluorescence spectrophotom-

eter was used for the determination of major and 23 trace elements concentration.
There is some basic difference in the nature of sediments of Marksnagar and
Durgajkhera. The sediments of Marksnagar are generally mud dominated with few
regular patches of kanker while that of Durgajkhera are sand dominated with kanker
formation invariably at depth below 18 meters. The basic mineralogy of the sand
fraction confirmed the dominant presence of quartz, muscovite, feldspar, and biotite
as major minerals with hornblende, garnet, tourmaline, kyanite, and epidote present
in trace amount.
Major Elements
Major element chemical composition of the bulk sediments of Marksnagar and

Durgajkhera indicates that these sediments mainly consists of three elements: Si,
Al, and Ca. Silica is dominant major component in the sediments of Marksnagar and
Durgajkhera as well as in the recent sediments of Ganga river and are 57.66%,
55.74%, and 73% respectively. The greater amount of Al2O3 was found at
Marksnagar where it was about 12% while CaO was only about 8%. But at
Durgajkhera, the average percentage of CaO is marginally higher than Al2O3; here
CaO is about 11.2% whereas Al2O3 is just about 10%. The relatively high percentage
of Ca in these bulk sediments is due to the extensive calcrete formation. The average
concentration of Al2O3 and CaO in the recent sediments was 11% and 1.5%,
respectively. The other dominant major elements are Fe2O3, K2O, and Na2O. The
average concentration of Fe2O3 varies from 3.8% at Durgjkhera to 4.6% at
Marksnagar. Not much variation was noted for the average concentration of MgO
in both the villages and was found to be about 3%. Marginally higher concentration
of K2O was found for Marksnagar where it was 2.73% while at Durgjkhera it was
only 2.35%. This difference in the concentration of K2O may be due to the difference
in the altered feldspar present in the sediments. The average concentration of Na2O
was about 1.4% at Marksnagar and 1.1% at Durgajkhera. In the modern sediment of
the Ganga river, the average concentration of Fe2O3, MgO, Na2O, and K2O is about
3.7%, 1.8%, 1.4%, and 2.6%, respectively. The detailed sedimentology of the study
area suggests that the lithology of Marksnagar is mud dominated while in
Durgajkhera there is comparatively lesser Mud. Since high content of clay was
found at Marksnagar a relative higher percentage of Al2O3, Fe2O3, and K2O in the
sediments of Marksnagar were found.
Trace Elements
Trace elements behavior in the sediments is influenced by weathering, diagenesis,

sediment sorting, and hydrogeochemistry of the sediments. At Durgajkhera, Ba
ranges from 312 to 576 ppm while at Marksnagar it ranges between 377 and
564 ppm. However, the Ba content for the sediments of Ganga was also determined
as the maximum value found here was 610 ppm and the minimum was 302 ppm. The
variation in the concentration of Rb was 93–145 ppm at Durgajkhera and
102–185 ppm at Marksnagar. Similarly, Sr was also found to range between
113 and 435 ppm for Durgajkhera and 154 and 396 ppm for Marksnagar. The
concentration of copper, chromium, lanthanum, and lead is invariably low in these
sediments and is less than 50 ppm. A high amount of cesium up to 100 ppm is also
recorded in these sediments. Zirconium was found to be ranging between 118 and
246 ppm for Durgajkhera, and 164 and 301 ppm for Marksnagar. Zirconium is
known to be least mobile and insoluble thus it remains in sediments. The higher
concentration of Zr at Marksnagar is probably due to the higher degree of chemical
weathering at Marksnagar. Since the sediments of Marksnagar are mud dominated
while that of Durgajkhera contains higher amount of sand so a general trend of
higher concentration of trace elements is noted in the village Marksnagar in com-
parison to Durgajkhera indicating a marginal higher rate of weathering at
Marksnagar. Fritz (1988) had stated that biotite and perthetic microcline are the
important phases of fresh rocks, which are enriched in Ba and Rb. He further added
that the alteration of biotite results in the loss of Ba and enrichment of Rb. The
average concentration of Ba in Marksnagar is 482 ppm and at Durgajkhera is
441 ppm while Rb is 135 ppm at Marksnagar and at Durgajkhera it is 125 ppm.
Thus, the comparatively higher content of Ba and Rb at Marksnagar supports the
higher occurrence of biotite in Marksnagar. The relative higher average concentra-
tion of Cr and Ni suggests the higher content of clay in Marksnagar samples which is
a direct evidence of higher degree of weathering (Sharma and Rajamani 2001).
Slight higher concentration of Sr at Durgajkhera confirms the formation of calcrete.
Interelement Relationship Between Major Elements
The interelement relationships were plotted on the variation diagram considering

Al2O3 (Singh et al. 2005) and TiO2 (Sharma and Rajamani 2000) as relatively stable
phases. The positive trend of Al2O3, Fe2O3, and K2O with TiO2 indicates the
enrichment of these elements as the concentration of TiO2 increases. This is due to
the formation of secondary clay minerals such as illite, which is the result of the
weathering of mica and feldspar (Wilson 1987). Some amount of iron may also have
been released from heavy minerals. A better positive correlation of these elements is
seen at Marksnagar as compared to Durgajkhera. Both Na2O and SiO2 are mobile
elements and thus are lost due to their dissolution in the water while TiO2 being the
least mobile element remains in the sediments. This negative correlation is better
seen for Marksnagar indicating a comparative higher rate of the weathering in the
area. According to Middelburg et al. (1988), both Na and Ca (in silicate form)
decrease more rapidly than K and thus are depleted more than K. The negative trend
of Na2O and CaO while the positive trend of K2O with the TiO2 results from the
greater alteration rate of plagioclase as compared to that of K feldspar. However,
CaO does not show a good negative trend due to its secondary precipitation in the
form of calcrete in the area thus it is not lost due to dissolution in water while remains
230 A. Saxena
in the sediments as calcrete. In general, the relationship between TiO2 and CaO gives
a strong negative trend on weathering but due to calcrete formation no trend is seen
more at Durgajkhera.
The feldspar and mica weathering may lead to the formation of illite, which is the
dominant clay mineral in these sediments and controls the concentration of Al and K
as depicted by a positive correlation between K2O with Al2O3. The weathering/
alteration of biotite may be responsible for the presence of MgO in the sediments. As
compared to Na2O and CaO, K2O and MgO are less mobile and remain in the
sediments during the incipient weathering and only become mobile in the solution
during the latter stage of weathering. Bricker et al. (1967) also believe that biotite, an
alumino-silicate mineral, contain the magnesium, iron, and potassium; and is the
most abundant magnesian mineral in the rock.
A positive correlation between Al2O3 with Fe2O3 indicates that their source of
origin could be the alteration of biotite into aluminosilicates and Fe (III) oxides due
to biotite weathering (Appele and Postma 1993) and is as follows:
2K½Mg2 Fe ½AlSi3 O10 ðOHÞ2 þ 10H þ :5O2 þ 7H2 O

! Al2 Si2 O5 ðOHÞ4 þ 2Kþ þ 4Mg2þ þ 2FeðOHÞ3 þ 4H4 SiO4
A strong negative correlation of SiO2 with the major elements also indicates the
grain size control on the geochemistry of the sediments, higher the grain size higher
the silica content. This silica dilution effect lowers the concentration of other major
and trace element. At Marksnagar the negative correlation between SiO2 is better
seen with MgO, Fe2O3, Al2O3 and Na2O3.
Interelement Relationship Between Trace Elements
The elemental pairs like that of Ba-Ga, Ba-Rb, Ba-Zn, Zn-Cr, Cr-Ga, Zn-Th,Cr-V,
Zn- As, Zn- Cr, Zn-Cu, Zn-Rb, Zn-Ni, Zn-V, etc. show a very good positive
correlation. Zirconium which is the most stable trace element does not show a
remarkable correlation with any element except for thorium. It gives a strong
positive correlation with Th.
A relative better positive correlation between the trace elements at Marksnagar is
indicative of comparative higher degree of weathering and higher clay content.
Interelemental Relationship Between Major and Trace Elements
The variation diagram of few trace elements are plotted against the major elements
SiO2, Al2O3, and Fe2O3 to see the variation in their concentration in the sand and
mud fraction. SiO2 gives a negative correlation with the trace elements, e.g., a
negative correlation between Ba and SiO2 indicates that as the silica content of the
sediments increases then the trace elements in the sediments decrease. Thus, from
this behavior of trace elements and SiO2, it can be said that the trace elements are
more concentrated in the fine silt and clay sized fraction than the sand fraction
(Fig. 15).
The positive correlation of the trace elements such as Zn with Fe2O3 and
ultimately with Al2O3 and MgO indicates its common source in the smectite
group, may be sauconite, which is characterized by the presence of Al, Mg, Fe,
and Zn in its lattice. Zn is an essential element for growth, development, and
reproduction in all living systems of the biosphere and would be supporting the
crop productivity of the area.
Durgajkhera Marksnagar
Ba(ppm)
600
700 Ba(ppm) 500
600
500 400
400 300
300
200 200
100 100
0
0
0 20 40 60 80 0 20 40 60 80
SiO2(%) SiO2(%)
Durgajklhera Marksnagar
Rb Rb
200 200
150 150
100 100
50 50
0
0
0 5 10 15
0 5 10 15
Al2O3(%) Al2O3(%)
Marksnagar Marksnagar
Zn Zn
100 100
80 80
60 60
40
40
20
20 0
0 0 2 4 6
0 2 4 6
Fe2O3(%) Fe2O3(%)
Fig. 15 The inter elemental relationship between trace elements(in ppm) and major elements (%)
232 A. Saxena
Chemical Maturity of the Sediments
A-CN-K Diagram and Chemical Index of Alteration
To ascertain the chemical maturity of the sediments, various schemes have been
suggested such as CIW, CIPW, CIA, etc. For the study area, the CIA values scheme
has been selected.
Nesbitt and Young (1982) proposed the quantification of chemical weathering
intensity as the “Chemical Index of Alteration” (CIA) where:
h i
CIA ¼ Al2 O3 = Al2 O3 þ CaO☼ þ Na2 O þ K2 O 100
CaO☼: CaO in silicate form only (Nesbit et al. 1997).
Here the molecular proportions of the above elements are used for the calculation
of CIA of the samples. In case the CaO in silicate form is not available then it is
assumed to be equivalent to Na2O because Ca is lost more rapidly than Na during
weathering and it will give the CIA values lesser than that of Na (Singh 2004). Since
the study area dominantly contains calcrete in abundance, the values of CaO are
invariably greater than that of Na2O. Because of this, the values of CaO were
assumed to be equivalent to Na2O. A CIA value of 100 indicates intense chemical
weathering where all the alkali and alkaline earth elements are leached out of the
system whereas CIA values of 45–55 indicates virtually no weathering. The fresh
granodiorite composition is also considered to be very close to UCC and gives the
CIA value of 47–50. With the initiation of weathering, the Ca and Na component of
the sediments starts leaching out first, as both of these are highly mobile in nature
and the trend of the weathering is seen parallel to A-CN line of the A-CN-K diagram.
Then during the intermediate phase of weathering when the above trend reaches
close to the formation of illite, K which was stable in the incipient phase of
weathering also becomes mobile and the weathering trend starts moving toward
the apex, i.e., A corner of the A-CN-K diagram.
The CIA values of the sediment samples of Marksnagar and Durgajkhera are
given in Table 2. The CIA values of Marksnagar ranges from CIA values of
54.41–63.3 and that of Durgajkhera ranges from minimum 53.23 to the maximum
of 63.6. In Marksnagar, the minimum value of 54.4 was found at the depth of around
30 m, i.e., at this level there was virtually no weathering while the sediment
immediate after it, i.e., at 33 m of depth shows the maximum weathering. The
sediment samples of the Durgajkhera which are at shallower depth generally gave
a lower CIA values for the samples up to 15 m with the minimum of 53.23 at the
depth of 9 m, which was also found to be sandy horizon. The maximum value was
found to be at the depth of 33 m. To illustrate these results, the ternary variation
A-CN-K diagram was plotted for both the villages (see Figs. 16 and 17).
It can be seen from the above figure that there is a loss of the most mobile
elements, i.e., Na and Ca in the sediments as compared to the UCC. The weathering
Table 2 CIA values of S. No. CIA S. No. CIA

Marksnagar (M1–M15)
M1 60.634 D1 59.15
and Durgajkhera
(D1–D11) M2 60.9496 D2 57.595
M3 61.79 D3 53.23
M4 63.08 D4 54.54
M5 62.012 D5 59.54246
M6 62.327 D6 63.52664
M7 61.955 D7 61.80034
M8 60.68 D8 61.68221
M9 62.124 D9 62.8052
M10 54.413 D10 62.78137
M11 63.29 D 11 63.60445
M12 56.465
M13 58.34
M14 59.292
M15 58.56
Marksnagar
A
100
Kaolinite
Smectite Illite
Muscovite
Biotite
Plagioclase K Feldspar
50 50
UCC
100 100
CN K
Fig. 16 A-K-CN diagram for Marksnagar
trend was found running parallel to A–CN line. It is clear from the above figure that
as the chemical weathering progresses, the clay minerals are produced due to
dissociation of primary minerals into secondary clay minerals. During the incipient
234 A. Saxena
Durgajkhera
A
Kaolinite
Smectite Illite
Muscovite
Biotite
UCC
CN K
Fig. 17 A-K-CN diagram for Durgajkhera
weathering, Na and Ca are rapidly lost to the weathering solution and thus are not
retained by the clay minerals while K due to its nature of being adsorbed by the clay
minerals retain as the weathering product. This is due to the specific size and charge
characteristic of K that leads it to retain in the layer position of 2:1 type clay mineral,
i.e., illite, thus making it present in the sediments till the weathering of illite also
initiates. Thus, it can be said that K is stable during the incipient and moderate
weathering and is mobile at higher degree of weathering. The retention of K and loss
of Na and Ca with the progress of chemical weathering leads to the general trend of
A-CN parallel weathering for both the sites.
A-CN-K diagram was also plotted for the recent sediments collected from the
bank of Ganga river at Kanpur and Bithur. This ternary variation diagram for the
recent sediments is shown in Fig. 18. It was noted that the similar trend of the
weathering parallel to A-CN line was also noted for the recent sediments.
It can be concluded from the above studies that that weathering pattern is same on
the surface as well as at the depth. The age of the sediments as revealed by the carbon
dating is about 30,000 years at the depth of 30 m (personal communication from
Dr. C. Rajgopalan). This means that there is no remarkable change in the weathering
pattern for the last 30,000 years. Moreover, it is clear from the A-CN-K diagram for
both ancient sediments and recent sediments that the weathering trend active in the
area is A-CN parallel.
Ganga Sediments
A
Kaolinite
Smectite Illite
Muscovite
Blotite
UCC
CN K
Fig. 18 A-CN-K diagram for the recent sediments.
Relative Mobility of the Elements with Respect to Al2O3
Elemental Ratio for Major Elements
The chemical composition of the sediments is expected to demonstrate a well-

established concepts on the mobility of various elements during the weathering
(Berner and Berner 1996 in Singh et al. 2005). The elemental ratio refers to the
relative enrichment or depletion of the element with respect to the least mobile
element, Al. It is given by dividing the ratio of the element X and Al2O3 of the
sediment sample with the ratio of the same element content in the UCC, i.e.,
Element Ratio ðXÞ ¼ ½X=Al2 O3 ðsediment sampleÞ

X=Al2 O3 ðUCCÞ
X > 1 indicates enrichment

X < 1 indicates depletion
X = 1 indicates no change in relative abundance of the element
Figures 19 and 20 display the elemental ratios of the major elements of

the sediments of Marksnagar and Durgajkhera. As demonstrated in the figure,
236 A. Saxena
Marksnagar
5
4
Elemental Ratio
0
MgO
MnO
Na2O
Fe2O3
SiO2
P2O5
TiO2
K2O
CaO
M1 M2 M3 M4 M5 M6 M7 M8 M9 M10 M11
M12 M13 M14 M15
Fig. 19 Relative abundance of the elements at Marksnagar
16 Durgajkhera
15
14
13
12
11
Elemental Ratio
10
9
8
7
6
5
4
3
2
1
0
Fe2O3
Na2O
TiO2
P2O5
CaO
MgO
MnO
SiO2
K2O
D1 D2 D3 D4 D5 D6 D7 D8 D9 D10 D 11
Fig. 20 Relative abundance of the elements at Dugajkhera
the SiO2 content in the sediments of both the sites is found to be enriched. TiO2 is
considered relatively to be immobile and thus remains enriched in all the samples of
both the villages. Whereas Na2O, which is highly mobile (Singh 2004), shows a
relative depletion. Though CaO is also very mobile in nature but due to secondary
formation of calcrete a relative enrichment is seen for the calcium. Potassium is
considered to be less mobile than Na and thus generally shows enrichment. Mg also
shows a relative enrichment trend because of incipient weathering in area.
Thus, both Mg and K are preferentially adsorbed and tightly incorporated in clay
minerals of the sediments (Singh et al. 2005). It can also be seen that there is a
remarkable enrichment of both Fe2O3 and MnO. This is probably due to the
formation of clay minerals. During the mineral weathering in the area the SiO2, Na
and K originate by incongruent dissolution of feldspar while the magnesium, iron,
and potassium may be released from the biotite and ferromagnesium minerals.
Calcium may be derived from the dissolution of calcretes.
Chemical Mobility of Elements with Respect to Weathering
Weathering is a phenomenon that involves the wear and tear of the parent rock
material and the mobilization and redistribution of the major and trace elements
present in it. This mobilization and redistribution is fascinated by the process of
dissolution of primary minerals, formation of secondary minerals, transportation of
materials, and its coprecipitation. Titanium is relatively immobile during weathering
and thus could be used for the calculation of the chemical mobility of the major and
trace elements. The chemical mobility of an element is determined by plotting the
CIA values against the percentage change of the element with respect to TiO2. The
percentage change is calculated in terms of percentage increase or decrease of the
element X (of samples) with respect to X in UCC.
Percentage change ¼ fðX=TiO2 Þ sample

ðX=TiO2 Þ UCC 1g 100:
The increasing or decreasing trend of the variation diagrams plotted for percent-
age change of element X against its CIA value indicates the increase or decrease of
chemical mobility of that element. The chemical mobility of the major elements of
the sediments of the Marksnagar and Durgajkhera is given in Figs. 21 and 22.
From the above figures, it is clear that during the chemical weathering there is a
definite mobility in the major element concentrations. The significant increasing
trend of chemical mobility of Fe and Mg proves the instability of the biotite and
muscovite content of the sediments as these two minerals are the most important host
for Fe and Mg present in these sediments. This dissociation of biotite and muscovite
is due to the weathering process active in the area. The increasing trend of CaO
depicts that as the weathering progresses, the chemical mobility of Ca increases. This
may be due to aqueous dissociation and coprecipitation of the calcreate during the
weathering. Al2O3 shows neither decreasing nor increasing trend, rather it is parallel
to CIA and indicates that it is comparatively very stable during weathering. Silicon,
sodium, and potassium showed a decreasing trend of chemical mobility. The mobil-
ity of SiO2 is very important to understand as it plays an important role in soil
formation. It can also be concluded that sodium decreases more rapidly than
potassium. This is due to the greater alteration of plagioclase as compared to K
feldspar, which is also shown in the A-CN-K diagram. Another reason for this could
be that K is more preferentially adsorbed in the clay minerals and could also be
incorporated with the silicate minerals.
238 A. Saxena
0 0
50 55 60 65 50 55 60 65
-10
-10
-20
Fe2O3
Fe2O
-20
-30
-30 -40
-40 -50
CIA CIA
0 0
50 55 60 65 -10 50 55 60 65
-10
-20
K2O
-20
K2O
-30
-30
-40
-40 -50
-50 CIA CIA
Marksnagar
Durgajkhera
100 80
80 60
60 40
MgO
MgO
40 20
20
0
0
-20
50 55 60 65
50 55 60 65
CIA CIA
1000 150
800
600 100
CaO
CaO
400
200 50
0
-200 0
50 55 60 65 50 55 60 65
CIA CIA
Fig. 21 Chemical mobility of the major elements during the weathering process
100
0
50 55 60 65
-10
50
SiO2
-20
SiO2
0 -30
-40
-50 -50
50 55 60 65
CIA CIA
0 0
-10 50 55 60 65 50 55 60 65
-10
-20
-20
-30
P2O5
P2O5
-40 -30
-50 -40
-60
-50
CIA CIA
0 0
50 55 60 65 50 55 60 65
-20 -20
Na2O
-40
-40
Na2O
-60
-60
-80
-80
-100
CIA CIA
0 0
50 55 60 65 50 55 60 65
-10 -10
-20
Al2O3
-20
Al2O3
-30
-30
-40
-40
-50
-50
CIA CIA
Fig. 22 Chemical mobility of the major elements during the weathering process
240 A. Saxena
Distribution of Major Elements with Depth
The variation in the concentration of major elements with the depth was plotted on
the logarithmic variation diagrams. The value of the major elements are in percent-
age. However, the average concentration of fluoride (in ppm) for 2 years at the
respective depth was also depicted in the graph to search for any correlation between
the fluoride and the concentration of major elements in the sediments (Fig. 23).
It can be interpreted from the above figures that pair SiO2 and CaO, and TiO2 and
Na2O3, are inversely proportional to each other. In Marksnagar as the SiO2 decreases
with the depth, there is an increase of CaO and simultaneously the fluoride content in
the water of that depth zone (M2, M6, M11, and M15 at 6 m, 18 m, 33 m, and 45 m,
respectively; below the ground surface) also increases. While with the increase in the
SiO2 content, there is a decrease of CaO and the fluoride content in the water in those
depth zones decreases (i.e., at M3 and M10, which are in the depth zone of 6–9 m
and 27–30 m, respectively). A positive correlation in the variation of the
100 100
10
10
1
1 0.1
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
D 11
M1
M2
M3
M4
M5
M6
M7
M8
M9
M10
M11
M12
M13
M14
M15
F(ppm) SiO2 CaO F(ppm) SiO2 CaO
100 100
10
10
1
1
D10
D1
D2
D3
D4
D5
D6
D7
D8
D9
D 11
0.1
M1
M2
M3
M4
M5
M6
M7
M8
M9
M10
M11
M12
M13
M14
M15
F(ppm) Al2O3 Fe2O3

MgO K2O F(ppm) Al2O3 Fe2O3 MgO K2O
10 10
1 1
0.1
0.1
M10
M11
M12
M13
M14
M15
M1
M2
M3
M4
M5
M6
M7
M8
M9
D1
D2
D3
D4
D5
D10
D 11
D6
D7
D8
D9
F(ppm) TiO2
F(ppm) TiO2 Na2O Na2O
Fig. 23 Variation of major elements with depth

concentration of Al2O3, Fe2O3, MgO, and K2O along with the depth suggests that
the concentration of all these elements is controlled by the variation in grain size
characteristic of the sediments and the change in the rate of weathering. Moreover,
the increase in the content of Fe and Mg in the sediments indicates the higher content
of biotite which is also probably releasing the fluoride in the ground water due to its
alteration. The source of K and Al may be K feldspar or any other aluminosilicate.
The positive correlation of fluoride with the variation of these elements confirms its
release from the biotite, as fluoride is present in the lattice of biotite and could be
released during the weathering of this mineral. There is a general trend of decrease in
the concentration of all the major elements except for SiO2 and Na2O at the depth
interval of 27–30 m (M10) suggesting a comparative dominance of SiO2. This zone
also coincides with the low value of fluoride in the water. However, at depth interval
of 30–33 m (M11), there is a remarkable decrease of SiO2 and increase of other
major elements. The CIA value of M10 is 54 while that of M11 is 63 indicating the
incipient weathering phenomenon in the depth zone M11 while this phenomenon is
inactive in M10 resulting in much lower values of fluoride in the water at 27–30 m
(M10) of depth as compared to the water at 30–33 m of depth.
Weathering and Release of Fluoride in Groundwater
It was seen during the study of geochemistry of the sediments that the concentration
and mobility of both the major elements and the trace elements are controlled
directly or indirectly by the weathering processes. This is because these elements
are either the primary products or the secondary products of the weathering. So, an
attempt was made to correlate the fluoride content in the groundwater with the CIA
value at that depth for the samples of Marksnagar. Since this fluoride is believed to
be the weathering product of probably of muscovite or biotite or both and by the
chemical mobility and enrichment of Fe and Mg and enrichment of Al in the
sediments, it is indicated that the weathering of these two minerals is still active.
So, in order to understand the mobility of fluoride in the ground water with the
changing trend of the chemical weathering intensity, i.e., the CIA values, a graph is
plotted (Fig. 24).
It is evident from the above figure that there is a definite role of weathering in the
release of fluoride in ground water of the area. It is noted that as the CIA value
increases the fluoride content of the ground water also increases indicating the
positive correlation between the two. The correlation coefficient between the fluoride
content in the ground water and the CIA value at that depth zone for Marksnagar was
about 0.8. The maximum fluoride was released at 30–33 m (M11) of depth, and the
CIA value was also found maximum for this sample. The minimum fluoride was
released at the depth interval of 27–30 m (M10), which also coincides with the
minimum CIA values. However, at the depth interval of 6–9 m (M3), the fluoride
content decreases with some increase in CIA. This might be due to difference in
lithological character of the sediments at that depth.
242 A. Saxena
CIA vs Fluoride
6 64
62
5
60
4
(in water)
Fluoride
58
3 56
CIA
54
2
52
1
50
0 48
M2 M3 M6 M10 M11 M15
Sample (Marksnagar)
Fluoride (ppm) CIA
Fig. 24 Relationship between F and CIA with the variation in depth at Marksnagar
CIA vs Fluoride
3.5 F CIA 63
3 62
2.5
Fluoride (ppm )
61
2
CIA
60
1.5
59
1
0.5 58
0 57
MI (0-9m) MII( 9-18m) MIII(18-30m) MIV(30-396m) MV(39-45m)
Depth Zone
Fig. 25 Relationship between F and CIA with the variation in depth at Nawabganj block
On the basis of above findings, the whole study area was broadly divided into five
zones viz., MI(0–9 m), MII(9–18 m), MIII(18–30 m), MIV(30–39 m), and MV
(39–45 m). The average fluoride content in the ground water at the respective depth
were plotted against the average CIA values of these respective depths (Fig. 25).
From Fig. 25, it is inferred that the average content of fluoride is found to be
higher at the depth less than 10 m and which also coincides with the high CIA value
(about 61) indicating the weathering to be active. At the depth range of about
10–20 m, the CIA values are at record high indicating weathering to be in progress
and the average fluoride content at this depth was also found to be high. The fluoride
decreases at the zone III and is found to be within the permissible limits. This could
be possible due to the remarkable decrease in the CIA values, and as this CIA value
increases as seen in the zone IV there is again increase in the average fluoride content
of the water. The comparatively lower CIA value at the depth interval of 18–30 m
indicates the very poor or no weathering. The CIA value at this depth interval also
coincides with the sediment age of 20–30000 of years as revealed by the carbon
dating. Moreover, this period also happened to be the last event of global glaciation.
So, the role of the last event of global glaciation in the weathering and ultimately in
the release of fluoride could not be ruled out. However, the lower CIA values at the
depth interval of 39–45 m and high content of fluoride in the water could not be
explained out as this is an exceptional case and only one sample was available at this
depth.
The conclusions drawn from the above findings are summarized as follows:
• It is concluded that fluoride content in the ground water of the study area is
controlled by lithology as well as pH of the water.
• The problem of increasing fluoride content in groundwater is more prominent in
the areas of mud dominant lithology.
• The probable source that is releasing fluoride in to the groundwater is due to the
dissolution of mica minerals, specially muscovite and biotite.
• The optimum pH for the abrasion of muscovite is 7 and for biotite is 8. The pH of
the ground water of the study area was also found to fall within this range with an
average value of about 7.6 pH, thus providing the optimum environment of pH
that could facilitate the abrasion of both the minerals.
• The abundance of biotite, altered biotite, and chlorite in the mineralogy of the
study area reveals that the biotite may be releasing comparatively more fluoride in
groundwater than muscovite. The presence of kaolinite and vermiculite in the
clay also confirms the alteration of biotite and albite [as kaolinite is formed due to
alteration of biotite and albite and vermiculite is formed due to alteration of biotite
(Weijden and Weijden 1995).
• The sedimentological and mineralogical findings were confirmed by the geo-
chemical data. The high content of Fe2O3 and MgO in the sediments also
indicates the higher content of biotite. According to Acker and Bricker (1992),
the mineralogical compostion of biotite contains about 20.19% of Fe2O3 and
14.4% of MgO.
• The geochemical data and the CIA values indicate the incipient weathering in the
area and support the weathering of biotite to be more progressive than muscovite.
On the basis of the above studies, it is suggested that the fluoride is more released
in the groundwater of areas having mud-dominant lithology. The release of fluoride
was found to be controlled with the pH of the water and the rate of weathering. It is
inferred that the minerals releasing fluoride belongs to the mica group and are mainly
muscovite and biotite. The mineralogical and geochemical data indicated that the
release of fluoride from biotite is more eminent than muscovite.
244 A. Saxena
Cross-References

▶ Global Status of Nitrate Contamination in Groundwater: Its Occurrence, Health
Impacts, and Mitigation Measures
▶ Identification of the Source Mineral Releasing Arsenic in the Groundwater of the
Indo-Gangetic Plain, India
▶ Role of Bioremediation as a Low-Cost Adsorbent for Excessive Fluoride Removal
in Groundwater
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Identification of the Source Mineral
Releasing Arsenic in the Groundwater 10
of the Indo-Gangetic Plain, India
Pooja Goel
Contents
The Problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
Global Status of Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
Indian Status of Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
Health Impact Survey . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
Location of the Study Area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
Geology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
Geomorphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
Topography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
Collection of Water Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
Water Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
Sedimentology and Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
Installation of Piezometers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
Grain Size Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
Heavy Minerals Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
Chemical Maturity of the Sediments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
Variation of Arsenic with Depth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
Abstract
Indo-Gangetic alluvium is the largest alluvial plain in the world and from few
decades the problem of arsenic is highlighted in the area. The higher content of
arsenic in groundwater used for drinking purpose causes arsenicosis which later
become carcinogenesis. Ghazipur district is part of newer alluvium and is an area
centrally located in this gangetic alluvium. Very high content of arsenic is noted in
P. Goel (*)
Centre for Advanced Study in Geology, University of Lucknow, Lucknow, India

https://doi.org/10.1007/978-3-319-73645-7_129
248 P. Goel
the groundwater of this area and the people are using this water for their drinking
and domestic purposes. As a consequence of this they are seriously suffering from
the arsenicosis. Thus to understand the source mineral for the release of arsenic in
the groundwater sedimentological, mineralogical, and chemical study has been
undertaken for the sediments through XRD and XRF analysis. It can be con-
cluded from these studies that the source mineral for the releasing arsenic in the
groundwater of the area is arsenolite (As2O3).
Keywords
Arsenic contamination · Groundwater · Ghazipur district · Uttar Pradesh · Indo-
Gangetic alluvium · Source mineral · Arsenolite · XRD
Indo-Gangetic plain is the largest Quaternary alluvial plain of the world. It is a

foreland basin and the Himalayas act as the source of sediment for this Ganga plain.
The Indo-Gangetic plain can be subdivided into three domains from north to south,
i.e., upper, middle, and lower Indo-Gangetic plain. The sub-basin lies in the states of
Uttar Pradesh, Madhya Pradesh, Bihar, Rajasthan, West Bengal, Haryana, Himachal
Pradesh, and the Union Territory of Delhi. The drainage area of Uttar Pradesh is
294364 sq.km. Uttar Pradesh, is in the central part of the Indo-Gangetic plain, is
formed of thick Quaternary sediments resting unconformably over basement of
Bundelkhand Gneissic complex, Delhi, Vindhyan, and Marwar Supergroups except
in area close to sub-Himalayan Siwalik ranges in north. These Quaternary deposits
have been classified broadly into three lithostratigraphic units representing different
cycles of sedimentation in basins of varying dimensions and magnitude and are
classified as:
• Pre-Quaternary deposits
• Older alluvium
• Newer alluvium
The older alluvium is the regional high surface while the newer alluvium refers to
the river valley deposits and present flood plain deposits. The main river draining the
Indo-Gangetic alluvium is the axial river Ganges to which all the other rivers join in
a distinct pattern (Fig. 1). The principal tributaries joining the river are the Yamuna,
the Ramganga, the Ghaghra, the Gandak, the Kosi, the Mahananda, and the Sone.
Chambal and Betwa are the two important subtributaries. In the central alluvium
part, the river channel shows variety of forms, i.e., braided, slightly and highly
sinuous, anastomosing, and also meandering in nature.
The Problem
In Indo-Gangetic alluvium groundwater is mainly used for drinking purposes and for
last few decades some water quality-related problems are encountered in the Gangetic
plain. The groundwater is reported contaminated due to various chemical impurities
10 Identification of the Source Mineral Releasing Arsenic in the. . . 249
Fig. 1 Drainage pattern of Uttar Pradesh (Source: www.indiawaterportal.org/img/Basin-Ganga.jpg)
such as arsenic, iron, fluoride, and nitrate. In one of these contaminations, the arsenic
problem in groundwater is reported in the last two to three decades from West Bengal
and Bangladesh and from last 6 years it is reported from Uttar Pradesh in Ballia,
Ghazipur, and some other districts. Geologically, the Ghazipur district is differentiated
into older and newer alluvium and geomorphologically into upland and lowland.
The symptoms and signs that arsenic causes, due to regular intake of arsenic in
drinking water, are arsenicosis and melanosis in which dark and white spots occur on
the skin and in later cases it develops into keratosis in which the skin becomes hard
and forms nodules. It appears to differ between individuals, population groups, and
geographic areas. Thus, there is no universal definition of the disease caused by
arsenic. Long-term exposure to arsenic via drinking water causes cancer of the skin,
lungs, urinary bladder, and kidney, as well as other skin changes such as pigmenta-
tion changes and thickening (hyperkeratosis). Absorption of arsenic through the skin
is minimal and thus hand-washing, bathing, laundry, etc., with water containing
arsenic do not pose human health risk. The most commonly manifested disease so far
is skin lesions. Over the next decade, skin and internal cancers are likely to become
the principal human health concern arising from arsenic.
WHO established a provisional guideline value for arsenic which is 0.01 mg/L.
But on the criteria of health, the guideline value for arsenic in drinking water would
be less than 0.01 mg/L. Because the guideline value is restricted by measurement
limitations, and 0.01 mg/L is the realistic limit to measurement, this is termed a
provisional guideline value. The national standard of arsenic for drinking water in
India and Bangladesh is 0.05 mg/L which is the permissible limit.
250
P. Goel
Fig. 2 (continued)
Global Status of Arsenic
The welfare and development of a society are dependent on a safe drinking water
supply. Arsenic contamination of groundwater supply is a threat to human health in
many regions of the world. Arsenic contamination has now become a problem in
many parts of the world. Even though there are not much reliable data available on
exposure and health effects, it is clear that there are many countries in the world
where arsenic in drinking water has been detected at concentration greater than the
guideline value, 0.01 mg/L, or the prevailing national standard. These include
Argentina, Australia, Bangladesh, Chile, China, Hungary, India, Mexico, Peru,
Thailand, and the United States of America. Countries where adverse health effects
have been documented include Bangladesh, China, India (West Bengal), and the
United States of America (Fig. 2).
Worldwide the number of people affected have been very low and has not been as
dangerous as has been found in many villages in West Bengal, India, and Bangladesh.
Patients with melanosis, leucomelanosis, keratosis, hyperkeratosis, dorsum,
non-pitting edema, gangrene, and skin cancer have been identified. Among the
affected people, the most common presentations are melanosis (93.5%), keratosis
(68.3%), hyperkeratosis (37.6%), and depigmentation (leucomelanosis) (39.1%).
Cancers were found among 0.8% and actinic keratitis and Bowen’s disease are
identified among 3.1% cases. There is no medicine yet for chronic arsenic poisoning.
The only remedy is safe water, nutritious food, and physical exercise.
There is a strong correlation between the occurrence of arsenic and the surface
geology and geomorphology. The worst affected aquifers are the alluvial deposits
beneath the recent floodplains. The groundwater arsenic problem in Bangladesh
arises because of a combination of three factors: a source of arsenic (arsenic is
present in the aquifer sediments), mobilization (arsenic is released from the sedi-
ments to the groundwater), and transport (arsenic is flushed away in the natural
groundwater circulation).
During preliminary survey by the Jadavpur University, arsenic was found in the
groundwater of some villages of Ghazipur district. Karkatpur village of the Karanda
Block is severely affected by the arsenic contamination. The All India Institute of
Medical Sciences, New Delhi, also confirmed that people living in the Ballia district
of UP also have high level of arsenic in their blood, hair, nail, etc.
It is being suspected that the mechanism for the release of arsenic in the ground-
water is a geogenic process. In Bangladesh arsenic toxicity in groundwater of the
Ganges delta and some low-lying areas in the Bengal basin is confined to middle
Holocene sediments. The arsenic toxicity in the groundwater of the Bengal basin is
caused by its natural setting but also appears to be triggered by recent anthropogenic
activities (Acharyya et al. 1999). According to Saxena et al. (2004), arsenic confined
ä
Fig. 2 Distribution of documented world problems with As in Groundwater in major aquifers as

well as water and environmental problems related to mining and geothermal sources. Areas in blue
are lakes (Smedley and Kinniburgh 2002)
252 P. Goel
to the newer alluvium in the Ganga plain and occur in narrow entrenched flood
plains and arsenic occur in groundwater of Bangladesh in the form of Fe and Mn
oxides, organic matter, and sulfide and silicate phases, i.e., H3AsO3 (most toxic
species), H2AsO3, HAsO3, H3AsO4, H2AsO4, HAsO4, and for the release of arsenic
in groundwater reducing conditions are essential. In Askote formation
(in Pithoragarh district) the arsenopyrite found in abundance (http://cps-amu.org/
sf/ascot) and which is drained by river Gandak and weathering material comes
through it to the Gangetic plain. According to Sengupta et al. (2004), the geomor-
phological domains with different depositional styles regulate the pattern of distri-
bution of zones with widely different content of arsenic in groundwater. The high
arsenic zones occur as narrow sinuous strips confined to channel deposits.
Some workers correlate the relationship of arsenic with other metals such as iron,
sulfate, nitrate, manganese, and molybdenum depending on the releasing condition of the
arsenic from the sediment (Ohno et al. 2005). There are two contradictory hypotheses
about the mobilization of arsenic in the groundwater. According to the first hypothesis,
As-rich pyrite in the shallow aquifer is oxidized due to lowering of water table and
releases As to the overextraction of groundwater for irrigation (Mandal et al. 1996;
Mallick and Rajagopal 1996). The second hypothesis suggests that As is released due
to desorption from and/or reductive dissolution of the secondary Fe-and/or
Mn-oxyhydroxides, due to the prevailing anoxic conditions in the sedimentary aquifers
(Bhattacharya et al. 1996, 1997). The sulfate ion shows negative correlation with As
supporting the notion that arsenic contamination in groundwater mainly occurs under
reductive conditions (Ohno et al. 2005). Arsenic toxicity in groundwater in the Ganges
delta and some low-lying areas in the Bengal basin is confined to middle Holocene
sediments. Dissected terraces and highlands of Pleistocene and early Holocene deposits
are free of such problems. Arsenic-rich pyrite or other arsenic minerals are rare or absent
in the affected sediments. Arsenic appears to occur adsorbed on iron hydroxide-coated
sand grains and clay minerals and is transported in soluble form and co-precipitated with,
or is scavenged by, Fe(III) and Mn(IV) in the sediments. It became preferentially
entrapped in fine-grained and organic-rich sediments during mid-Holocene sea-level
rises in deltaic and some low-lying areas of the Bengal basin. It was liberated subse-
quently under reducing conditions and mediated further by microbial action. Intensive
extraction of groundwater for irrigation and application of phosphate fertilizer possibly
triggered the recent release of arsenic to groundwater (Acharyya et al. 1999). According
to Singh I. B. 2008, The Ganga Alluvial Plain is a significant geochemical linkage
between the source (the Himalaya) and the sink (the Bay of Bengal).
The source of arsenic in deltaic plain of West Bengal is considered to be the
arsenic-rich sediments transported from the Chotonagpur Rajmahal Highlands
(Acharyya et al. 2000; Saha et al. 1997) and deposited in sluggish meandering
streams under reducing conditions. No detailed groundwater analysis for arsenic is
available for the Middle and Upper Ganga Plains. It is hypothesized that the arsenic
problem involves the entire Gangetic Plain as the geology of Middle and Upper
Ganga Plains are similar (Chakraborti et al. 2003).
High concentration of arsenic is found in groundwater hosted by the sediments in
close proximity to the meander segments where the lithology is represented by
successions of gravel, coarse to medium sand, fine sand, silt, and clay (PHED 1991;
Bhattacharya et al. 1997). Narrow and isolated tracts of As-polluted areas are reported
from adjoining parts of the Bihar, eastern Uttar Pradesh (U. P.), and northern tip of
Jharkhand States, which are located in the middle section of the Ganga alluvial plain
(Acharyya and Shah 2004). The As-contaminated areas, in the Ganga plain, are
exclusively confined to the Newer alluvium (Holocene) and occur in narrow
entrenched flood plains, where sedimentation was influenced by sea level fluctuation
during the Holocene causing increased aggradation and forming fluvial swamps
(Singh 2001a). The vast interfluve upland terraces, covering around 90% of the
Central Ganga alluvium plain, where older alluvium is either exposed or occurs
under shallow newer alluvium cover (Kumar et al. 1996; Kumar 2003) are unlikely
to be As-polluted. For the interpretation of the ancient sediment and environment;
mineralogical assemblage are the key to it (Kumar and Singh 1978).
Arsenic-rich sediments derived from the Himalayan mountains and the foothills
of the Shillong Plateau are deposited in the Gangetic Plain, Padma–Meghna–B-
rahmaputra delta of Bangladesh, Terai region of Nepal, Chandigarh area, and now
Bihar. The deposition is expected to be in the Holocene-type deposits. The meander-
ing pattern of the river is responsible for the localized depositions of arsenic rich
sediment in selected areas along the course of the river Ganga. Whether the huge
groundwater withdrawal, pivotal to the green revolution, allows oxygen to enter into
the aquifer, initiating microbial activities, or has any relation to localized increases in
arsenic mobilization is yet to be understood (Chakraborti et al. 2003).
Indian Status of Arsenic
Arsenic calamity in India was first known in West Bengal during 1978–1980 and
was officially documented by K. C. Saha from the School of Tropical Medicine,
Calcutta, in 1983 (unpublished data). Arsenic contamination in groundwater and
sufferings of the people of West Bengal are well documented in 1984 by Garai et al.
and Saha by reporting patients suffering from arsenical skin lesions in Nadia,
Murshidabad, Malda, Barddhaman, and North and South 24-Parganas districts. Garai
et al. reported the first scientific paper published on arsenic toxicity in West Bengal. This
problem is from 20 years in West Bengal even then many persons who are drinking
contaminated water are not aware of this problem and its consequences (Fig. 3).
The School of Environmental Studies (SOES), Jadavpur University, joined the
arsenic work at the beginning of 1988. Jadavpur University surveyed West Bengal in
1988 and found 22 villages of 5 districts are arsenic affected, and when the survey
was again done in 2005 the problem emerges on a large scale and 3510 villages are
found affected and many villages are yet not surveyed. Jadavpur University reported
that ingestion of arsenic contaminated water with 300 μg/L for prolonged period may
cause arsenical skin lesions.
It was known that West Bengal and Bangladesh had high levels of arsenic in the
groundwater, but slowly the problem is spreading to other states like Uttar Pradesh,
Bihar, and Assam.
254 P. Goel
Fig. 3 Density of population affected by arsenic in India (Source: www.rgs.org/RGS-IBG-SITE/

Templates/Level3.asp)
The problem of arsenic in the Gangetic alluvium in Uttar Pradesh has been
brought into the notice in 2003 in three blocks of Ballia district and later in 2005
in the district of Ghazipur. In 2002 the arsenic was reported in Bihar from one village
of Bhojpur district and in 2005, 73 villages from three districts are found to be
arsenic contaminated. As reported by Jadavpur University the Chain Chapra village
of Belhari Block, District Ballia, Uttar Pradesh, is one of the severe arsenic contam-
inated villages and people are suffering from arsenic toxicity. In the year 2003 the
arsenic was highlighted in Ballia district of Uttar Pradesh and after that in 2005 two
other districts Ghazipur and Benaras are found to be affected by arsenic contamina-
tion in groundwater. The groundwater across Uttar Pradesh shows an alarming level
of arsenic contamination, which is increasing spatially with time and more and more
Fig. 4 Groundwater arsenic

contamination in three
districts of Uttar Pradesh
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Fig. 5 Variation of arsenic concentration in water sample in pre-monsoon 2006

256 P. Goel
Fig. 6 (a and b) Photograph of 16-year-old Saddam of Karkatpur Village showing skin lesions on
the chest due to high intake of arsenic in the drinking water
areas of Uttar Pradesh are being engulfed with this problem. It is being suspected that
the mechanism for the release of arsenic in the groundwater is a geogenic process.
As by preliminary survey it was found that the concentration of arsenic is high in
the groundwater of Karkatpur Village which is in the newer alluvium, and to know
the reason that from where and how it is releasing in the groundwater the detailed
study of sedimentology and mineralogy is done. The other village Chochakpur
which lies in older alluvium is also selected for the comparative study (Fig. 4).
Health Impact Survey
Based on secondary data the preliminary survey for the Karkatpur village, Karanda
Block, Ghazipur district, was done in June 2006 to know the severity of the problem
(Fig. 5). The survey indicates high content of arsenic in groundwater of the area. The
analysis was done by arsenic monitoring kit provided by the UNICEF in collabora-
tion with U.P. Jal Nigam. Almost all the water samples collected from the Mark II
hand pumps installed at about 30 m of depth were tested and showed high concen-
tration of arsenic in them.
The regular intake of arsenic in the drinking water causes arsenicosis and
melanosis in which dark and white spots occur on the skin, and in later cases it
develops into keratosis in which the skin becomes hard and forms nodules. The
symptoms and signs of arsenicosis appear to differ between individuals, popula-
tion groups, and geographic areas. Thus there is no universal definition of the
disease caused by arsenic. It is a fatal disease as it causes cancer. The health
impact survey conducted in the study area (Karkatpur village, Karanda Block,
Ghazipur district) shows that all age groups of villagers are being adversely
Fig. 7 Photograph of
23-year-old Achelal of
Karkatpur Village showing
skin lesions on his stomach;
he is suffering from this
disease for last 4 years
affected by ailments of arsenic. Figs. 6, 7, and 8 show the adverse effect due to
the high intake of arsenic in their drinking water.
Location of the Study Area

The study area lies between the latitude 25 200 N to 25 300N and longitude 83 250 E

to 83 350 E partially falling in the Survey of India toposheet no.63 O\7 & 63 O\11.
Being located in the plains of Ganges the soil is alluvial type and is fertile because of
low level floods continually replenishing the soil. This makes agriculture the most
important profession of the people. On the whole the area is a fertile plain and all the
three types of crops viz. kharif, rabi and zaid are grown here. The main crops grown
here are rice millets, barley, wheat, mustard, maize, etc. Beside these crops horti-
culture is also prominent in the area. Ghazipur is situated in the eastern part of Uttar
Pradesh; hence the climate of Ghazipur is not very hot or cold. It enjoys subtropical
climate with moderate annual rainfall. The temperature varies from 5 C to 17 C in
winters and 30 C to 42 C in summers. But sometimes winter temperature ebbs to
3 C and summer temperature shoots up to 45 C. The annual rainfall in the district
was between 800 mm. On average there are 49–55 rainy days (days with rainfall of
2.5 mm or more) in a year in the district (Fig. 9).
258 P. Goel
Fig. 8 Photograph of 60-year-old Yaseen of Karkatpur Village showing skin lesions on his (a):
palm, (b): chest, (c): stomach, and (d): back
Geology
The Ganga Plain extends from Aravalli-Delhi ridge in the west to the Rajmahal hills
in the east. The Himalayan foothills (Siwaliks) lie in the north of it while the
Bundelkhand-Vindhyan Plateau is in south, occupying an overall area of about
250,000 sq km (after Singh et al. 1996). The catchment area of the Ganga Plain
has distinct lithostratigraphic units from north to south, i.e., Central Crystalline
Group, Simla Group, Krol Belt, and Siwalik Group. Because of its setting in front
of the rising Himalayas, a huge sediment load is brought into the basin which is
again redistributed by the fluvial processes. The source rock of sediments of the
Ganga Plain are granites, gneisses, quartzites, schists, limestones, slates, sandstones,
phyllites, greywackes, and siltstones.
Singh et al. (1996) divided the Ganga plain foreland basin into three subdivisions:
(a) Peidmount Plain Located adjacent to the Himalayan mountain belt, where the
sediment fill is in direct response to the thrust-fold tectonics, flexed lithosphere,
and subsidence.
Fig. 9 (a and b) Location map of Ghazipur district and study area

260 P. Goel
Fig. 10 Geological setting of the study area (after Singh 1992)
(b) Central Alluvial Plain It shows most of the south and south west flowing
drainage swinging, in general, to south east and east direction. All the major
rivers from Himalayas follow this trend and their southern bank shows Piedmont
cliff and escarpments.
(c) Marginal Alluvial Plain It forms the southernmost part of the Ganga plain, and
is characterized by restricted thickness of alluvium over the basement, hence the
control of structural features of the basement on the drainage network is quite
common (Singh 1992).
The study area is the part of Central alluvial plain where the general trend of
Ganga river is NW-SE, which is also the tectonic lineament direction of Central
alluvial plain. According to Hakim et al. (2001) the basement of the area is
granite, which ranges in depth from 250 to 600 m. The sediments belonging to
Neogene and Quaternary overlie the granites (Fig. 10).
The lithostratigraphy of the area (Singh 2001a) is as follows:
Recent
Holocene alluvium Micaceous sand and silt
Newer Cyclic sequence of silt, clay, and micaceous sand
alluvium
Disconformity
Mid–Late Pleistocene Varanasi Polycyclic sequence of sand, silt, and clay with
older ferruginous and calcareous concretion
alluvium
Unconformity
(continued)
Recent
Holocene alluvium Micaceous sand and silt
Late Pliocene to Banda older Medium to coarse gravel, sand with clay and silt
Early–Mid Pleistocene alluvium
Unconformity
Basement of Bundelkhand granite gneiss and Vindhyan sediments in the south

and Siwalik (?) in the north.
Geologically, the study area exposes Quaternary sediments which are differenti-
ated into older and newer alluvium. The older alluvium, termed as Varanasi alluvium
(Middle to Late Pleistocene age), contains polycyclic sequence of silt, clay with
kankar layers, and subordinate beds/lenses of micaceous sand. The newer alluvium
(Holocene age) occupies lowland and is divisible into terrace alluvium and channel
alluvium. The terrace alluvium consists of interbeded sequence of grey sand, silt, and
clay and is well exposed in Muhammadabad-Zamania sector along Ganga river. It is
also present along Chhoti Sarju nadi and Gomati river. The channel alluvium
includes loose sand of point/channel bars and mud flats of flood plain of Ganga
and Gomati rivers. Thin layers of mud occupying palaeochannels are considered as
homotaxial to the Newer Alluvium (Fig. 11).
Figure 12 gives the geological map of the study area showing the location of the
study area in Karkatpur and Chochakpur.
Geomorphology
Geomorphologically, it is differentiated into upland and lowland. The upland,

known as Varanasi plain, lies in Ganga-Ghaghara interfluve with elevations of
69–82 m above msl. The ground of Varanasi Plain is silty to clayey, slopes gently
towards east, and has relict fluvial features in the form of tals and palaeochannels.
The lowland, lying 2–10 m below the adjacent upland along Ganga, Chhoti Sarju,
and Gomati rivers, contains Older Flood Plain (Terrace Plain) and Active Flood
Plain (Channel Plain). Two levels of traces (T1 and T1a ) are developed along Ganga
whereas one level of terrace (T1) is present along Gomati and Chhoti Sarju. These
terraces are of depositional type and preserve the sediments deposited by these rivers
in the form of point/channel/lateral bars. It is wide and sandy along Ganga but
narrow and silty along Chhoti Sarju and Gomati. According to Singh (1992) this
alluvial plain has a gentle consistent regional slope and a narrow range of grain sizes
but the channel shows a variety of forms namely braided, slightly sinuous, highly
sinuous, anastomosing, oxbow lakes, (Fig. 13) etc.
Topography
The general slope of district is from north-west to south-west, this being the direction
generally taken by subsidiary drainage lines though the Ganga itself leaves the district
in a higher latitude than at its point of entry, while north-easterly course of Karmnasa
262 P. Goel
Fig. 11 Geological map of Ghazipur district (Source: GSI Resource map)
points to the existence of a reversed slope on the south bank of the Ganga. The soil and
the general topography of district depend directly on the drainage. A Digital Elevation
Model (DEM) of the Ghazipur district was prepared using SRTM data of 90 m
resolution. The data was free to download from the internet. The data was downloaded
and a DEM was prepared for the whole district of Ghazipur. It was found that the NW
part of the district is at higher elevation than Eastern part of the district. We get a better
view of DEM in three-dimensional (3-D) view (Fig. 14).
The above figure clearly depicts the topography of the Ghazipur district. The
number of drains and rivers could be seen in the upper half of the district joining the
Ganga river. Similarly in the lower half also some streams are confluencing into the
Ganga river indicating that on surface slope is towards river Ganga and the regional
slope seems to be NW to SE. However, a slope map was prepared for the study area
Fig. 12 Geological map of study area (Adopted from Geological Resource Map of Ghazipur
published by GSI, Northern Region, 2001). Karkatpur village is shown by “dot” whereas
Chochakpur village is shown by “square”
Fig. 13 Pictorial view of meandering loop of Ganga River at Karkatpur Village, Karanda Block,
Ghazipur district
using the SRTM data of Ghazipur district. This slope map was prepared by pro-
cessing the 90 m resolution SRTM data on ArcGIS software. Figure 15 gives the
slope map of the study area.
264 P. Goel
Fig. 14 DEM (3D view) of Ghazipur district
Legend
slope_90m (in degrees)
Value
0 – 0.5
0.5 – 1.0
> 1.0
0 3,625 7,250 14,500 21,750 29,000
Meters
Fig. 15 Slope map of the study area
It can be seen from the above slope map that in general the area has a very gentle
slope of less than 1.0o. However, around Ganga river there is a steep slope at both the
left and right bank of the river. Moreover the slope along streams confluencing into
the Ganga also shows the slope greater than 1o increasing towards Ganga River.
Number of palaeochannels and oxbow lakes can be seen around the Ganga River. In
general the regional slope of the study area is from NE to SW.
Collection of Water Samples
The representative water samples from all the depth zones tapped for drinking
purposes were collected from various villages (Karkatpur, Chochakpur, Karanda,
Dhammarpur, etc.). There are three different zones tapped viz. shallow zone (i.e., for
dug well, generally up to 20 m bgl), middle zone (where hand pumps (named Mark
II) are installed at about 30 m bgl), and deep zone (where tube wells are installed at
>40 m of depth). Although majority of the population use Mark II hand pumps
installed by UP Jal Nigam (government organization for PHED) for the drinking
purposes a few use tube wells also. These users are those who generally own these
private tube wells and have installed for their irrigation purposes. For last couple of
years very few numbers of people use the dug wells for their domestic needs.
Water Quality
The water sampling was done in the pre monsoon period 2008 so that there should be
minimum effect of dilution due to the rain water. The water samples have been taken
mainly from Chochakpur (falling in older alluvium of Gangetic Plain) and from
Karkatpur (falling in newer alluvium of Gangetic Plain), so that we can get the
quality status of groundwater in the alluviums of different geologic age, i.e., older
and newer alluvium and some variation in sedimentology was also expected. These
water samples include water sample from Mark II hand pumps, tube wells, and dug
wells, i.e., for tapping different depth. The water quality analysis was done to know
the severity of the problem in the area. The water quality analysis includes various
parameters like pH, TDS, Ca, Mg, Na, K, and some heavy metals but here we discuss
only arsenic and iron. This water is potable and mainly used for drinking purposes so
the adverse impact on environment and health due to higher/lower concentration of
these elements in the water from their desirable limits as per BIS or WHO norms is
also done.
Arsenic
Arsenic can be found naturally on earth in small concentrations. It occurs in soil

and minerals and it may enter air, water, and land through wind-blown dust and
water run-off. Arsenic is one of the most toxic elements that can be found. Humans
may be exposed to arsenic through food, water, and air. Exposure may also occur
through skin contact with soil or water that contains arsenic. Exposure to arsenic
can cause various health effects, such as irritation of the stomach and intestines,
decreased production of red and white blood cells, skin changes, and lung irrita-
tion. It is suggested that the uptake of significant amounts of inorganic arsenic can
intensify the chances of cancer development, especially the chances of develop-
ment of skin cancer, lung cancer, liver cancer, and lymphatic cancer. A very high
exposure to arsenic can cause infertility and miscarriages with women, and it can
266 P. Goel
cause skin disturbances, declined resistance to infections, heart disruptions, and

brain damage with both men and women. Finally, inorganic arsenic can
damage DNA.
Arsenic-related illness is usually caused by consumption of contaminated
drinking water. Arsenic appears to be essential for some plant and animal species.
A possible safe dose for humans was calculated. If arsenic is a dietary mineral, this
dose would be 15–25 μg. This amount could be absorbed from food without any
trouble. The total amount of arsenic in a human body is about 0.5–15 mg. Many
arsenic compounds are absorbed 60–90%, but they are also easily excreted.
Humans can develop resistance to certain arsenic concentrations. Shortly after
absorption arsenic can be found in liver, spleen, lungs, and digestive tract. Most
arsenic is excreted, and residues may be found in skin, hair, nails, legs, and teeth.
Under conditions of prolonged exposure, many organs may be damaged, skin
pigmentation may occur, hair may fall out, and nail growth may stop. Arsenic-
related health effects are usually not acute, but mostly encompass cancer, mainly
skin cancer. Arsenic may cause low birth weight and spontaneous abortion.
Arsenic in drinking water is an issue of global importance, therefore the WHO
limit was decreased to 10 ppb, and however as per BIS norms this limit is still
50 ppb.
The variation of arsenic in the ground water samples collected from the study area
was plotted and compared with the 50 ppb permissible limit of BIS norms. Figure 16
shows this variation.
It can be clearly seen from the above graph that the high concentration of arsenic
is mainly found in the samples of Karkatpur village (Sample 1-A to 7-A and 14-A). It
has been noted that the concentration of arsenic in all the water samples taken from
the Mark II hand pumps installed at Karkatpur village is high above the permissible
limit whereas the water samples taken from the hand pumps of the other areas like
Chochakpur (11-A and 12-A), Karanda (13-A), Dhammarpur (9-A), etc., show low
concentration of arsenic. It was also found that water samples taken from the dug
well (2-A) and tube well (8-A) at Karkatpur are also not contaminated from the high
concentration of arsenic. This means that shallow water table and deep water table
Fig. 16 Arsenic variation at $UVHQLF

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represented by dug well and tube well respectively are not contaminated by arsenic.
Whereas the aquifer tapped for the installation of hand pumps (mainly 20–30 m bgl)
are highly contaminated by arsenic.
The rural population living in the study area mainly uses the hand pumps for their
drinking purposes and other domestic uses. The prolonged use of the groundwater
contaminated with high arsenic content has caused the adverse effect on the health of
these people. The above figure shows an example of Karkatpur village that the
villagers using arsenic contaminated water for their domestic and drinking purposes
are eventually affected by arsenocosis and are suffering from skin diseases. The
unawareness and unavailability of the alternative source of drinking water force
many of the people living in Karkatpur to use the arsenic-contaminated hand pumps.
Iron
Iron is believed to be the tenth most abundant element in the universe. The main
naturally occurring iron minerals are magnetite, hematite, goethite, and siderite.
Weathering processes release the element into waters. Iron is essential to almost
living things, from microorganisms to humans. The total amount of iron in the
human body is approximately 4 g, of which 70% is present in red blood coloring
agents. When high concentrations of iron are absorbed, for example, by
hemochromatose patients, iron is stored in the pancreas, the liver, the spleen, and
the heart. This may damage these vital organs.
The water samples collected for the analysis of iron showed a positive correlation
with the arsenic content in the ground water. Although the concentration of iron in
the groundwater was well within the BIS norm of 300 ppb, it was found that the iron
content in the water samples of Karkatpur village (especially water collected from
hand pumps) was high as compared to the other sites. Figure 17 shows a case of high
iron content in the groundwater causing the red staining of the floor.
Fig. 17 Red staining of

concrete floor indicative of
high iron content at Karkatpur
268 P. Goel
Fig. 18 Iron variation at ,URQ

Karanda block

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The concentration of iron in the water samples of dug well and deep tube well was
very low. Figure 18 shows that pattern of high concentration of iron in the ground
water is similar to that of arsenic. It is noted that the sampling sites showing higher
value of arsenic are also showing high iron content. Thus a probable positive
correlation between the arsenic and iron could not be ruled out and may be both
these elements are releasing from the same mineral and mechanism.
By the above study some relevant information comes out that the problem of high
concentration of arsenic is mainly sporadic in nature and is mainly in the shallow
aquifer of Karkatpur where the hand pumps are installed at the depth of 20–30 m of
depth and are used for drinking purposes. Moreover, the water of dug well and tube
well, i.e., shallower and deeper aquifer are also arsenic free. Other areas were also
found to be not affected by high concentration of arsenic. The positive correlation of
arsenic with iron is also noted. The arsenic concentration was also very low for the
water samples of tube well which was installed at the depth of about 40 m and thus
this water could also be used for drinking purposes. To find any possible correlation
between the high content in the ground water and the respective sediments a detailed
sedimentological, mineralogical, and geochemical analysis was done.
Sedimentology and Mineralogy
The study includes the subsurface geology of the area, one of the area lies in the
newer alluvium and the other in the older alluvium of the Indo-Gangetic Plain. The
problem of arsenic is encountered in the newer alluvium and probably has some
source in the sediment of the area, i.e., the problem of arsenic is geogenic in nature.
So the main objective of the study is to decipher the natural source of arsenic in the
study area that leads to the leaching of arsenic into the groundwater. Attempts are
also made to identify the depth zones which are responsible for the release of Arsenic
into the shallow aquifers. This necessitated the sedimentological and mineralogical
study of the sediments up to the maximum depth to which the piezometers have been
installed.
Installation of Piezometers
Two piezometers were installed to get the vertical profile variation of the sediments
up to a depth of 36 m by the interval of 3-m distance. One piezometer was installed
in the Karkatpur and second one was installed at Chochakpur village which is in the
older alluvium. Karkatpur is in the newer alluvium which is only 500 m from the
meandering channel of river Ganga. During the installation of piezometers the
lithologs of the vertical profile was prepared (Fig. 19).
Our focus was also on the identification and characterization of clay minerals by
using X-Ray powder diffraction (XRD) to know the source of arsenic in the
groundwater of the study area. The sedimentology and mineralogy was done for
the sediments collected at the time of installation of the piezometers. The grain size
mbgl
mbgl
Legends
0–3 0–3
Clay+Silt
3–6 3–6
6–9 6–9
Silt (with some kanker and gravel)
9–12 9–12
12–15 12–15
Gravel with Sand
15–18 15–18
18–21 18–21 Silty Sand
21–24 21–24
Fine Sand (with some silt)

24–27 24–27
27–30 27–30
Fine to Medium Sand
30–33 30–33
33–36 33–36
Karkatpur Chochakpur
Fig. 19 Strata charts prepared during the installation of piezometers
270 P. Goel
analysis of the sediments was done to identify the dominance of sand, silt, and clay.
The mineralogy of the coarser fraction, i.e., 120 mesh, was done with the help of
petrological microscope and for the finer fraction, i.e., clay, it was done with the help
of XRD. In all 12 samples each from both the sites were collected for Karkatpur
(newer alluvium) and Chochakpur (older alluvium) and two samples were collected
from active channel of Ganga river (recent), i.e., in total 26 sediment samples were
collected for grain size and mineralogical studies.
Grain Size Analysis
Grain size analysis was done for 24 sediment samples collected during the installation of
piezometer at Karkatpur and Chochakpur. Twelve samples at the interval of 3 m are
taken from Karkatpur (samples named as A1 to A12) and from Chochakpur (samples
named from C1 to C12). In Chochakpur it was found that the sediments are mud
dominant and contain 71% of mud by weight while sand fraction (with some kanker in
traces) was found to be only 29%. The general lithology at Karkatpur is sand dominant
with average of 58% of sand in all the samples. Bar diagrams of a few representative
samples of Karkatpur and Chochakpur were plotted. It was found that the sediments of
Karkatpur and Chochakpur showed almost the similar pattern up to the sample number
A1 to A7 at Karkatpur and C1 to C7 at Chochakpur, i.e., up till the depth of 21 m from
surface. This pattern mainly indicates the dominance of mud, i.e., clay and silt fraction in
these sediments. However, the sample C3 of Chochakpur at the depth of 6–9 m showed
an abruptly high percentage of gravel (with kanker) in its sediments.
In general the dominant lithology at Chochakpur is mud and at Karkatpur it is sand
(mainly medium sand). As already mentioned at Chochakpur the average sediment
fraction is broadly made up of 29% of sand (with gravel and kanker) and 71% of mud
by weight, but on further division of this mud fraction into silt and clay it was found
that on an average the mud fraction is made up of about 85% of silt whereas clay
was present only up to 15%. The average grain size at Karkatpur shows 58% of sand
and 42% of mud. Further the separation of mud into silt and clay using sedimentation
cylinder shows about 95% of silt and rest 5% of clay present at Karkatpur.
Heavy Minerals Identification
The heavy mineral identification was done after separation of heavy minerals from
quartz, feldspar, and mica minerals using bromoform. However, small fraction of
mica minerals and feldspar could not be separated from the rest of the heavy
minerals. The main heavy minerals identified in the sample A11 (30–33 m bgl at
Karkatpur) are biotite, garnet, hornblende, muscovite, amphibole, sillimanite,
enstaite, feldspar, and apatite, and arsenolite-like mineral (botryoidal and isotropic)
was also identified. Samples like A9 (24–27 m) and A7 (18–21 m) at Karkatpur
showed the same heavy minerals as stated above except for arsenolite (Fig. 20).
Fig. 20 (continued)
272 P. Goel
Fig. 20 Photographs of minerals identified under petrological microscope
Mineralogical Composition of Clay

For the mineral identification, samples were analyzed through XRD technique to
know that which mineral is responsible for the source of the arsenic in the ground-
water of the study area and whether there is any difference in the mineralogy of both
the newer and older alluvium. Samples of clay separated through sedimentation
cylinder were analyzed for Karkatpur and in addition to that heavy mineral samples
were also analyzed for Karkatpur. Clay samples of Chochakpur were also analyzed.
One sample of Ganga sand was also analyzed through XRD technique for the
mineral identification.
The sample analyzed for Karkatpur A 11 (normal ) at the depth of 30–33 m below
ground level (bgl) was showing major peak of quartz, prominent peak of calcite at
3.023 Å and chlorite at 7.08 Å & 3.52 Å. The other mineral compound identified in
this sample was calcite, sodium alum, and clinochlore. A very prominent peak of
arsenolite (As2O3 ) at 3.19 Å, 6.45 Å, 2.76 Å, and 1.95 Å was identified which could
be the source mineral for arsenic in the groundwater of the area.
The sediment sample representing the depth interval of 30–33 mbgl in
Chochakpur (C11) was analyzed, which is also a sandy zone and most of the hand
pumps used for drinking purposes installed at this depth show major peak at 9.92 Å
confirming the presence of illite. The peaks of saponite, chlorite, calcite, clinochlore
and sericite were also found in these samples, confirming the presence of these
minerals also.
However, a detailed analysis and minerals identified through XRD analysis are
given in the figure below.
As described earlier that 0–5% of the clay by weight was found in the sediment
samples of Karkatpur while at Chochakpur it was present up to 15%. The clay
minerals identified in the samples of both the sites broadly belongs to the mica,
smectite, chlorite, and kaolinite group with the peak of illite/mica group to be the
most strong.
Mineralogy of Heavy Minerals

The XRD for heavy minerals were done for the two samples of Karkatpur to confirm
the heavy minerals that have been identified through the identification of clay
minerals by XRD technique. The sample selected for this analysis was C11 at
depth 30–33 m respectively. The basic reason for the selection of the sample of
this depth was that mostly the arsenic contaminated hand pumps used for drinking
purposes are installed at the depth of 30 m, thus the sample number A11 was
selected.
The minerals identified in the heavy mineral sample for A11 (Figure 21d, e) were
mainly depended on the d-spacing. The peak of quartz at 3.34 and 4.26 Å were
identified along with chlorite at 7.08 and 3.52 Å, illite at 9.9 Å, and arsenolite
mainly at 3.19 and 2.26. Along with this muscovite-2 m and clinochlore were also
identified in this sample.
Ganga sand collected from the bank of river near Karkatpur was also analyzed
through XRD for understanding the mineralogy of the recent sediments and finding
any possible correlation with other samples. The major peak of muscovite/illite was
found at 9.9 Å followed by chlorite at 7 and 4.2 Å; microcline was also detected at
3.24 Å. The other minerals identified were nimite, kaoline, sillimanite, calcite, and
dolomite. Few peaks of arsenolite along with albite were also detected at 3.19, 3.9,
3.34, and 3.32 Å.
274 P. Goel
Analysis of Water Samples Through XRD

All five water samples were analyzed through XRD technique to understand the
minerals and compound dissolved in water. Firstly the water samples were dried at
40–45 oC in the oven and then the residual material left after complete evaporation of
water is analyzed for the presence of minerals and/or compound dissolved in water.
For this five water samples were analyzed representing the site highly contaminated
with arsenic (Kw1), dug well (Kw2), tube well (Kw8), etc. The description of sample
with location is given in following Table 1.
As described earlier all the water samples taken from Mark II hand pumps were
found to be contaminated with arsenic while the dug well water sample representing
the shallow aquifer and the water sample taken from the tube well representing the
deeper aquifer were not affected by the high concentration of arsenic. Figure 22
gives the X- Ray diffractogram for the sample Kw1.
On the analysis of Kw1 sample major peak of talc was detected followed by peaks
for calcite, quartz, and kaolonite. At 3.17 Å a peak of albite was noted. The peaks at
3.19 Å, 6.3 Å, and 2.26 Å indicate the presence of arsenolite in the sample. Another
arsenic bearing mineral named as Urusovite (CuAlAsO5) was also identified in this
sample. The arsenic content in water in this sample was very high and the sediment
sample representing this depth zone (30–33 m) also shows some arsenic-bearing
minerals.
The another sample analyzed was Kw2 which is of dug well showed no arsenic-
bearing mineral. Major peak of sylvite (KCl) at 3.14 Å was identified along with
trona and aphthitalite (at 2.84, 2.94, 4.09, 3.67, and 2.04 Å); another mineral
identified in this sample was halite. Similarly the major mineral identified in Kw6
sample was calcite (calcite magnesium), quartz, and halite (NaCl). The sample
representing the tube well water, i.e., Kw8, showed a major peak of barite at
3.42 Å, and another major peak of sodium nitrate at 3.07 and 3.06 Å were detected.
Hamatite was detected at 2.71 Å. Aragonite and apatite are the other minerals
identified in this sample. This analysis suggests that the probable mineral contam-
inating the groundwater with the arsenic at the depth of 30–36 m at Karkatpur could
be mainly due to presence of arsenolite.
Chemical Maturity of the Sediments
A-CN-K Diagrams and Chemical Index of Alteration

Nasbitt and Young (1982) proposed the quantification of chemical weathering
intensity as the “Chemical Index of Alteration” (CIA) for finding the maturity of
various sediments where:
h i
CIA ¼ Al2 O3 = Al2 O3 þ CaO☼ þ Na2 O þ K2 O 100
CaO☼: CaO in silicate form only (Nesbit et al. 1997).

Here the molecular proportions of the above elements are used for the calculation
of CIA of the samples. In case the CaO in silicate form is not available then it is
Fig. 21 (continued)
276 P. Goel
Fig. 21 (continued)
assumed to be equivalent to Na2O because Ca is lost more rapidly than Na during

weathering and it will give the CIA values lesser than that of Na (Singh 2004). Since the
study area dominantly contains calcrete in abundance therefore the values of CaO is
invariably greater than that of Na2O. Because of this the values of CaO were assumed to
be equivalent to Na2O. A CIA value of 100 indicates intense chemical weathering where
all the alkali and alkaline earth elements are leached out of the system whereas CIA
Table 1 Sample Arsenic

details of water Sample Type Location contamination
samples analyzed
Kw1 Mark II hand Karkatpur Very high
through XRD
pump
Kw2 Dug well Karkatpur Nd
Kw4 Mark II hand Karkatpur High
pump
Kw6 Mark II hand Karkatpur High
pump
Kw8 Tube well Karkatpur Nd
nd not detected
Fig. 22 XRD analysis of sample Kw1 evaporated sample of water for mineral/compound
identification
Fig. 21 (a) XRD analysis of sample C11 (30–33 m depth) at Chochakpur. (b) XRD analysis of
sample of heavy mineral for A9 (9–12 m depth) at Karkatpur. (c) XRD analysis of sample A11
(30–33 m depth) at Karkatpur. (d) XRD analysis of sample A11 (30–33 m depth) for heavy minerals
at Karkatpur. (e) XRD analysis of sample A11 (30–33 m depth) for heavy minerals (with identified
peaks) at Karkatpur. (f) XRD analysis of sample Ganga sand for heavy minerals near Karkatpur
278 P. Goel
values of 45–55 indicate virtually no weathering. The fresh granodiorite composition is

also considered to be very close to UCC and gives the CIA value of 47~50. With the
initiation of weathering, the Ca and Na component of the sediments starts leaching out
first, as both of these are highly mobile in nature and the trend of the weathering is seen
parallel to A-CN line of the A-CN-K diagram. Then during the intermediate phase of
weathering when the above trend reaches close to the formation of illite, K which was
stable in the incipient phase of weathering also becomes mobile, and the weathering
trend starts moving towards the apex, i.e., A corner of the A-CN-K diagram.
Figure 23 shows the A-CN-K graph plotted for Karkatpur. The A-CN-K diagram
shows that the trend of weathering is parallel to A-CN line. It can be seen from the
above figure that there is a loss of the most mobile elements, i.e., Na and Ca in the
sediments as compared to the UCC. The weathering trend was found running
parallel to A-CN line. It is clear from the above figure that as the chemical
weathering progresses then the clay minerals are produced due to dissociation of
primary minerals into secondary clay minerals. During the incipient weathering, Na
and Ca are rapidly lost to the weathering solution and thus are not retained by the
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clay minerals while K due to its nature of being adsorbed by the clay minerals retain
as the weathering product. This is due to the specific size and charge characteristic of
K that leads it to retain in the layer position of 2:1 type clay mineral, i.e., illite, thus
making it present in the sediments till the weathering of illite also initiates. Thus it
can be said that K is stable during the incipient and moderate weathering and is
mobile at higher degree of weathering. The retention of K and loss of Na and Ca with
the progress of chemical weathering leads to the general trend of A-CN parallel
weathering for both the sites. Thus the nature of weathering at Karkatpur seems to be
of incipient type with average CIA values less than 65.
A ternary plot was plotted for Chochakpur as shown in Fig. 24. The trend was
found to be parallel to the A-CN line of the A-CN-K diagram. The A-CN-K diagram
for Chochakpur shows that in general for most of the samples the rate of weathering
seems to be of moderate to intermediate phase as the trend appears to be close to the
formation of illite. The A-CN-K diagram plotted for Karkatpur and Chochakpur
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280 P. Goel
shows that the rate of weathering active in the Karkatpur is of incipient nature
whereas the rate of weathering at Chochakpur is close to its intermediate phase.
This is also confirmed by presence of more clay and silt at Chochakpur than at
Karkatpur.
A-CN-K diagram was also plotted for the recent sediments collected from the
bank of Ganga river at Karkatpur. The sample includes the sand fraction as well as
the suspended sediments collected from the above said location of Ganga River. This
ternary variation diagram for the recent sediments is shown in Fig. 25. It was noted
that the similar trend of the weathering parallel to A-CN line was also noted for the
recent sediments.
It can be concluded from the above studies that weathering pattern is same on the
surface and active at the depth. However, slightly higher rate of weathering was
noted at Chochakpur as compared to Karkatpur of surface sediments of Ganga river.
Ternary Plot of Ganga

A (Al2O3)
0 100
tite
10 90
ec
Illi
Sm
te
20 80
Muscovite
30 70
40 60
Biotite
Plagioclase
50 50
K Feldspar
60 UCC 40
70 30
80 20
90 10
100 0
0 10 20 30 40 50 60 70 80 90 100
CN (CaO+Na2O) K (K2O)
Fig. 25 A ternary plot for Ganga sediments

Variation of Arsenic with Depth
Figure 26 shows the variation of arsenic with depth at Karkatpur and Chochakpur. The
concentration of arsenic was plotted against the depth shows that there is not much
variation in its concentration except at the depth interval of 30–33 m at Karkatpur.
The concentration of arsenic in the sediments were found to vary between 29 to
83 ppm and 27 to 90 ppm at Karkatpur and Chochakpur, respectively. However, at
depth interval of 30–33 m at Karkatpur it was found that there was abrupt increase in
the concentration of arsenic. This finding has been confirmed by XRD analysis done
for the heavy minerals at this depth which shows the peak of arsenolite (AsO2) at this
depth which confirms the presence of high concentration of arsenic at this depth.
Moreover, the water samples taken from this depth also shows very high concen-
tration of arsenic, correlating the above findings with each other.
The analysis of water samples showed that the problem of high concentration of
arsenic is mainly sporadic in nature and is mainly in the shallow aquifer of Karkatpur
where the hand pumps are installed at the depth of 20–30 m of depth and are used for
drinking purposes. The water of dug well and tube well, i.e., shallower and deeper
aquifer, are arsenic free. Moreover, the ground water samples collected from the other
areas of Karanda block lying in the older alluvium were also found to be without any
arsenic contamination. A positive correlation of arsenic with iron was noted. The
arsenic content in the dug well water was very low and thus this water could be used as
alternative source of drinking water. The arsenic concentration was also very low for
the water samples of tube wells which were installed at the depth of about 40 m and
thus this water could also be used for drinking purposes.
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Fig. 26 Variation of arsenic with depth at Karkatpur and Chochakpur

282 P. Goel
The concentration of arsenic in the sediments of Chochakpur and Karkatpur were

found to vary between 29 to 83 ppm and 27 to 90 ppm at Karkatpur and Chochakpur
respectively. However, at depth interval of 30–33 m at Karkatpur it was found that
there was abrupt increase in the concentration of arsenic and was found to be
227 ppm. This finding has been confirmed by XRD analysis done for the heavy
minerals at this depth which shows the peak of arsenolite (As2O3) at this depth which
confirms the presence of high concentration of arsenic at this depth.
Thus it can be concluded from the above studies that problem of high concen-
tration of arsenic in the groundwater of Ghazipur district is mainly in the newer
alluvium along the large meandering loop of river Ganga and the main mineral
probably responsible for the high content of arsenic in the groundwater could be due
to the presence of arsenolite.
Cross-References
▶ Fluoride Contamination in Groundwater and the Source Mineral Releasing

Fluoride in Groundwater of Indo-Gangetic Alluvium, India
▶ Global Status of Nitrate Contamination in Groundwater: Its Occurrence, Health
▶ Micro-remediation of Metals: A New Frontier in Bioremediation
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Industrial Solid Waste Management in a
Developing Country Governorate and the 11
Opportunities for the Application of
Cleaner Production Principles
Aida O. Al-Batnij, Issam A. Al-Khatib, and Stamatia Kontogianni
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
The Study Area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
The Study Means . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
Characteristics of the Questionnaire Respondents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
SWM Practices on Locality Level . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
SWM Practices on Factory Level . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
Conclusions and Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Abstract
Hebron is an industrial governorate south of Palestine where the lack of studies
ends up to inexistent evaluation of its environmental status. Understanding the
status of industrial solid waste management (SWM) largely contributes to the
determination of the opportunities and the appropriate roadmap for the applica-
tion of cleaner production principles.
In this chapter, we report the results of an extended research-constructed survey
conducted in Hebron both at municipal level and industrial level. Primarily the
A. O. Al-Batnij (*)
Faculty of Graduate Studies, Birzeit University, Birzeit, Palestine
I. A. Al-Khatib
Institute of Environmental and Water Studies, Birzeit University, Birzeit, West Bank, Palestine
S. Kontogianni
Laboratory of Heat Transfer and Environmental Engineering, Department of Mechanical
Engineering, Aristotle University of Thessaloniki, Thessaloniki, Greece
e-mail: kontogst@auth.gr

https://doi.org/10.1007/978-3-319-73645-7_144
286 A. O. Al-Batnij et al.
municipal level research was aimed at identifying the current SWM practices. Then
the industrial level research was aimed to collect data on both the applied SWM
practices in local industries and record the generated quantities of ISW.
Towards the development, updating and implementation of a legislative frame-
work, which will support an integrated SWM in the local industrial area, the
stakeholders are highly encouraged to develop an incentive system for industries
to reduce and recycle the generated ISW. This need clearly emerges from the
current research results: Only 21 out of 91 factories treat SW before final disposal;
83.33% of them recycle the waste in situ or in collaboration with local recycling
stakeholders; 51.65% of the investigated industries produce a mixture of process
and nonprocess ISW, the average rate of nonprocess ISW is 23.22 kg/day; 8.4% of
factories always separate process ISW from nonprocess ISW; 85.7% of factories do
not separate their ISW into specific components. Only 13.6% of factories reuse and
16.5% recycle ISW; 77.3% of the recyclable materials are used as secondary raw
materials, and 22.7% of them use the separated ISW as secondary raw materials in
production, both implementing the fundamental 3Rs principle.
Keywords
Industrial solid waste · Field research · Cleaner production · Collection · Policy
Introduction
Developing the industry sector means achieving a high rate of economic growth,
creating many job opportunities and increased economic diversification necessary to
achieve general economic and social growth.
Developing countries has many pressing problems of poverty, population, hunger,
water, sanitation, public health, or ethnic and political strife, so proper environmental
management has not been considered as key issue in these countries. Competing
priorities of municipalities often consider other public works programs more important
than solid waste management improvements, not-to-mention industrial waste manage-
ment. In these countries, hazardous wastes have not received sufficient due attention. In
many countries, industrial wastes, both hazardous and nonhazardous wastes, are still
handled and disposed of together with domestic wastes and thus posing great health
risks to municipal staff, the public, and the environment (Mato and Kaseva 1999).
Cleaner production can be defined as “the continuous application of an integrated
preventive environmental strategy to processes, products, and services to increase
overall efficiency, and reduce risks to humans and the environment” (Abbasi and
Abbasi 2004; Žarković et al. 2011). “Cleaner Production can be applied to the
processes used in any industry, to products themselves and to various services
provided in society” (UNDP 2002). Waste minimization, reduction at source, pol-
lution prevention, eco-efficiency, etc. are synonyms for cleaner production
(Shkoukani 2008; Cagno et al. 2005).
The main goal of the performed research presented in this chapter was to evaluate
the existing SWM practices and assess the opportunities for the application of
11 Industrial Solid Waste Management in a Developing Country Governorate. . . 287
cleaner production principles in six industrial categories in Hebron governorate.

Towards this, the current ISW management practices on localities and factories
levels were examined and the level of services provided was accessed. Additionally
the quantities of ISW generated were estimated and the opportunities of practicing
cleaner production (to recycle and reuse of ISW) in industries and the readiness of
the owners and managers for that were identified.
Background
Across the world, a growing commitment to sustainable development is leading to

businesses reassessing their management practices. Cleaner production is now the
basis for industries’ approach to waste avoidance. Increasingly companies are
looking beyond compliance and are focusing their investments to optimize both
environmental and economic outcomes. The role of government in these changes is
to set the signposts, to map out the pathways for the future and to provide a safety net
for when systems fail (EPA 1998).
Different industrial sectors have applied cleaner production concepts as preven-
tive measures in order to increase eco-efficiency, reduce risks to both humans and the
environment, and save natural resources since people are becoming increasingly
aware, more than ever, of shortages in natural resources and of increases in air, land,
and water pollution (Abbasi and Abbasi 2004). Waste minimization techniques can
provide long-term benefits to industries such as waste reduction, promoting a
positive public image, improving product quality, improving the health and safety
of employees, cost savings, improved compliance, process and operation efficiency,
and reducing liabilities (Taylor 2006; Petek and Glavic 1996).
Developed countries have established legislation to deal with such problems,
while for developing countries such legislation and polices have still been under
processing, and some countries cannot even create an action plan to deal with
industrial pollution (Al-Qaydi 2006). Developed countries are busy in developing
and implementing waste-to-energy technologies associated with energy recovery,
composting for waste avoidance, and recycling and reuse, while developing coun-
tries are still struggling to decide on the best options to treat and dispose of waste
(Mrayyan and Hamdi 2006).
Industrial solid waste management forms an essential issue that related directly with
public health and environment. Industrial wastes vary considerably in quality and degree
of seriousness, depending on the type of industry, manufacturing methods, and material
used. An advanced system of industrial solid waste management is composed of several
functional elements. In such a system, all steps of management from the generation
of waste to the final disposal step are considered carefully. The different
functional elements of modern industrial waste management are generation and storage,
pollution prevention and waste minimization, recycling and reusing, collection and
transferring, treatment, and disposal (LaGrega et al. 2001; Mokhtarani et al. 2006). The
aforementioned were taken into consideration and were embedded in the field research
performed.
Methodology
The Study Area
The study area is Hebron governorate which is bounded by Bethlehem district from
the north and by the 1948 green line from the other directions; it is located in the
southern part of the West Bank at about 36 km to the south of Jerusalem, Palestine.
Hebron governorate is the largest one in the West Bank in terms of size and
population; total population of Hebron governorate was 551,130 persons which
represent 14.7% of the total population of Palestine; the large number of population
indicates large number of housing units, so Hebron governorate contains 103,086
housing unit (PCBS 2008).
Economic Situation in the Governorate

Hebron district is one of the most economically active districts, with its exports
reaching 10.75 million dollars, out of the 39.3 million dollars of the overall Pales-
tinian exports, as stated by a statement by the Palestinian Federation of commerce
chambers on December 3, 2008 (Hilal and Salaymeh 2011).
The Palestinian industrial sector developed significantly and increased its share in
GDP after the creation of the Palestinian Authority in 1994 from 13.3% in 1994 to
16.5% in 1998 (Hilal and Salaymeh 2011), while this percentage decreased to 14.6%
in 2003, according to the Palestinian Central Bureau of Statistics 2001. The contri-
bution of the industrial production to Palestinian GDP was 15.3%, 14.9%, and
14.6% in 2007, 2008, and 2009, respectively (PCBS 2010).
The economic situation in the Hebron governorate moves through a fluctuation
range and depends, to the large extent, on the stability of the political situations. The
industrial sector still suffers from dependence on Israeli industry which has affected
its development and growth. In addition, the procedures and practices of Israel since
2000 such as closures and the Israeli military siege on Palestinian areas in the West
Bank and Gaza Strip had negative impact on Palestinian industrial sector; productive
ability dropped in all Palestinian industries and in all governorates of the West Bank
and Gaza Strip, and the industrial sector sustained much damage because of the siege
and its impact on the movement of people and goods, the increase in time, the
associated costs, and creating unpredictability in trade flows and market shrinkages
(World Bank 2007; Hilal and Salaymeh 2011). Another difficulty that Palestinian
industries suffer from is the reliance of many of them on Israeli and foreign raw
materials, which leads to rising production costs, reduces the quality of the product,
and makes these industries vulnerable to changes and the political situation, resulting
in the decline of these industries (Hilal and Salaymeh 2011).
The Palestinian industry sector consists of three main activities: mining and
quarrying (extractive industries), manufacturing, and supply of electricity, gas, and
water. Manufacturing is considered the largest branch of the industrial sector,
accounting for more than 95.8% of its facilities (Hilal and Salaymeh 2011).
The advantage of Hebron is the availability of one of the most important
components of any industry: raw materials, where it is endowed with raw materials
for food industries (agricultural products and milk) as well as leather (livestock in the
governorate) in addition to raw materials for the construction industries (stone,
marble, and remnants of cut stone), and also cosmetics and other crafts, these
industries could provide economic opportunities, according to the situation of the
governorate; complementary services to industries in general also provide an impor-
tant economic opportunity, particularly those that support them through marketing
and packaging and those that provide design work for the timber, mineral, and
leather industries (Hilal and Salaymeh 2011). The majority of establishments of
the industrial sector were found to be micro, small, and medium enterprises, and
these industrial facilities face many problems in the areas of administration, finance,
marketing, and packaging (Hilal and Salaymeh 2011).
SWM in the Study Area

Solid waste management services are usually the responsibility of the municipalities
and local or village councils in Palestinian urban and rural areas. In the refugee
camps, the United Nations Relief and Works Agency for the Palestinian Refugees in
the Near East (UNRWA) is the body responsible for providing solid waste manage-
ment services (Khatib and Al-Khateeb 2009). There are a number of communities,
however, for which there is no municipal authority or village council; approximately
12% of communities in Hebron District fall into this category (Southern West Bank
Joint Service Council for Solid Waste Management 2009).
Management of industrial solid waste is distinctly different from the approach
used for municipal waste. There is a lot of similarity between the characteristics of
the waste from one municipality or one region and another, but for industrial waste,
however, only a few industrial sectors or plants have a high degree of similarity
between products and waste generated. Nowadays, industrial solid waste manage-
ment is an important part of industry. The number of contaminated sites, which are
polluted by industrial and hazardous waste, are increasing in developing countries
(LaGrega et al. 2001). For proper management of industrial waste, it is necessary to
obtain exact information and data about the waste characteristics, climatic condi-
tions, and the effects on human health and the environment (Mokhtarani et al. 2006).
The Study Means
Data was collected using structured questionnaires; the first one addressed the
localities that are responsible to manage industrial solid waste and the second one
the factory representatives/stakeholders.
The collected data included:
• Estimation of the quantities of ISW generated from the six industrial categories
(paper, plastic, metals, textiles, plants, chemicals, others)
• Rating of indicators involved with:
• Temporary storage processes
• Collection and transfer processes
• Treatment and final disposal processes

• Clean product process
• Safety and security processes
• Policy obstacles for cleaner product
• Financial obstacles for cleaner product
• Technical obstacles for cleaner product
• Administrative obstacles for cleaner product
The retrieved data was analyzed using the Statistical Package for Social Science
(SPSS version 12) program and Microsoft Office Excel. Descriptive statistics such as
frequencies and percentages were computed.
Results and Discussion
Characteristics of the Questionnaire Respondents
Localities: Τhere are 17 municipalities and one local council which is Nuba council;
one of the municipalities was excluded from analysis because it had no factories; this
municipality is Kharas. So the total localities included in this study are 17. Most
respondent’s positions were head of health section which accounted for 59% of the
respondents. Ninety-four percent of them were male, and 6% were female (engi-
neers). Results related to education level of respondents revealed that 14 out of 17
have high education, and the other 3 have secondary level.
Factories’ representatives: Among 91 respondents, 96.2% of respondents were
male, and 3.8% were female. Most respondents reside in the city (93.7%) and 6.3%
reside in villages. Results related to education level of respondents revealed that
53.2% have high education, 38% have secondary education, and the other 8.8% have
elementary education. Seventy-three percent of respondents were owner of the
factory, 9.4% manager, 9.4% production manager, and 8.2% were human resource,
financial, and quality manager and labors.
Factories characteristics: Forty-nine percent of factories are modern since
they had been established after 1999; 30.8% of factories have less than 10 labors,
41.8% have 10 to 19 labors, 24.2% have 20 to 99 labors, and 3.3 have more than
99 labors. The highest percentage (73.6%) of factories located in the city between
houses, while 20.7% in the city in the industrial area, 4.6% in villages, and 1.1%
in commercial area. So it is clear that the choices of factories locations
in Palestinian territories are not based on a structured master plan; so existing
highest percent of (73.6%) factories within residential areas are posing higher
pollution and more public health risk for the people who are living near factories.
Forty-three percent of factories were individual ownership, and 57% were private
joint-stock company. Figure 1 shows the factories products distribution of the
survey sample.
Fig. 1 Factories products

distribution of the survey primary
sample chemicals
plastics; 14;
industry; 5; 6%
15%
food and
drinks; 25;
27%
primary
metals
industry; 16;
18% textiles; 17;
19%
paper
industry; 14;
15%
SWM Practices on Locality Level
ISW Collection and Transferring

In Hebron governorate, the community container collection system is the main
common practice used in the solid waste collection and storage; the percent of
collecting solid wastes from the factories was 100%. Hebron, Beit Ula, Taffuh,
and BanyNa’im municipalities declined that industrial waste is collected with
domestic waste (constituting 23.5%), but the other 13 municipalities confirmed
that (76.5%).
There were no special containers for ISW in the study area, excluding six factories
in Hebron city. Although these factories have special containers for temporary
storage of their wastes, 100% of municipality’slaborers are responsible for collecting
and transferring waste from factory to Yatta dumpsite. This is completely different
compared to Dar es Salaam City, since 40% of ISW is collected by private SWM
contractors, while the individual industries collect and transport their own waste (the
remaining 60%) (Mbuligwe and Kaseva 2006).
Hebron, Surif, Beit Ula, Taffuh, Sa’ir, and Dura municipalities have different
vehicles for the transport of industrial solid waste that account for 37.5% of the
respondent localities; the remaining localities use the same as the domestic waste
collection vehicles (62.5%).
Vehicles used for collecting and transporting ISW are mainly in the range of
5–25 m3. Each of the localities participating in the survey have 12 special vehicles in
the range of 7–25 m3 and 28 compressor vehicles in the range of 5–18 m3 for long-
range transport, 9 of them in the Hebron city alone. They are generally self-tipping
trucks and are used because of their versatility with respect to unloading the waste at
the final disposal site. Loading of the waste is normally done mechanically or mixed
(manually and mechanically), according to the results: the percentages of solid
wastes that are loaded inside the vehicles manually, mechanically, and mixed were
5.9%, 23.5%, and 70.6% respectively. It is worth noting that some of the ISW
collection vehicles are not specially designed for that purpose. The vehicles fleets
of the localities are all covered vehicles (70.6%), or some of them have covers
(17.6%), while in 11.8% of the cases, they have no covers.
52.94% of localities face thresholds and bottlenecks in collecting and transferring
ISW from factories, which are summarized to be the absence of coordination with
the locality, increase of ISW quantities, vehicles and containers’ limited number,
ISW disposal in nonconfirmed locations, ISW unsuitable for truck loading (semi
liquid), long distance between temporal storage/disposal and final disposal leading to
high transferring cost, and lack of control.
ISW Temporal Storage

In the study areas, researchers found out that there is no separation between
industrial and domestic solid wastes at all. Beit Ula, Taffuh, Tarqumia, Dura, and
BanyNa’im municipalities have a temporary storage of ISW before final disposal
(29.4%), while 70.6% do not. Hebron and Tarqumia municipalities answered that
there are industrial solid waste transfer stations before final disposal, but the majority
of localities denied it.
For 15 out of 17 localities it is an easy task to locate containers near factories area,
but in 94% of the cases those containers have no covers. Hebron, Surif, Halhoul, and
Edh Dhahiriya seem to have no problems with adequate size of the containers (given
the waste generation from nearby factories) that accounts for only 25% of the
respondents. Ninety-four percent of the respondent localities confirmed the existence
of bad odors, insects, or rodents near to SW storage containers that are potential to
cause negative impacts on both the health and environment.
ISW Treatment, Processing, and Final Disposal

Cleaning, separation and classification, separation of hazardous components, reuse,
and recycling are the usual methods of ISW treatment. In the area where the field
research took place, the ISW are not treated at all.
Currently, most of the solid waste from Hebron governorate and from some
villages in Bethlehem governorate is dumped at the dumping site at Yatta. Solid
waste from Israeli settlements in Hebron and from the UNRWA-managed refugee
camps and some industrial waste are also taken to the dumpsite (Southern West Bank
Joint Service Council for Solid Waste Management 2009). Referring to the results of
this study, all the collected wastes from the included localities have been dumped at
Yatta dumpsite. Landfilling is still the cheapest and most common method of both
industrial and municipal waste disposal in Poland. Incineration, composting, and
neutralization are other utilization methods of wastes but in small scales (Jurczak
2001); while the final disposal of ISW in Dar es Salaam city are in Vingunguti and
Mbagala municipal disposal sites, the proportion of the industries that use these
disposal sites are 56.9% and 37.9%, respectively, and 5.2% of industries use onsite
disposal (Mbuligwe and Kaseva 2006).
Yatta dumpsite has been used to dump wastes since 1994 and has been
managed by Higher Council for SWM for Hebron and Bethlehem Governorates.
The dumpsite is located southeast of Hebron city, near the town of Yatta and has a
total area of 150 dunums without fencing around. There are nine employers working
on the site and it has weighing bridge to weigh the loaded trucks entered the site.
According to Alsari’, about 20 ton/day of industrial wastes enter the site, and they
get 16 NIS/ton whatever the type of wastes. There were 17 dumpsites in Hebron
governorate, 11 out of them were closed by Higher Council for Solid Waste
Management for Hebron and Bethlehem Governorates and the others with Yatta
dumpsite will be closed when Al-Minya landfill start operating in the middle of
2013; the landfill will be divided into eight cells (none of them is specialized for
ISW); one for every 2–3 years operation (Higher Council for SWM 2012). Al-Minya
landfill with a total area of 254 dunums is currently under construction, and it is
located to the east of Se’ir; it is financed by the World Bank and the European Union
with 20 million dollar (Hebron Municipality 2012).
Coordination Between Localities and Authorities

The results showed that there is a good coordination between the respondent
localities and other authorities related to management of ISW, and 76.5% of respon-
dent localities said that there is coordination with health department and JSC.
Surif, Halhoul, and Yatta municipalities that accounted for 30% of respondent
localities said that they impose regulations related to management of ISW to the
factories; the other 70% said that such regulations are imposed by other authorities
such as EQA and MNE; the results showed that almost 70% of regulations were
imposed by EQA and 30% by MNE. In the absence of regulation application some
penalties are imposed, the result explained that 43% of penalties were financial,
21.4% were postponed or canceled factory licensing, 7% were closure of the factory,
and 28.6% were all of them together. And in order to check the validity of these
answers, the participants were asked whether any penalties were applied during their
work performance; the majority (75%) confirmed that and 25% of them did not.
Financial Aspects
It is well known that most localities have financial constraints regarding SW
sector, in addition to political conditions that significantly affect providing the
services; the lack of proper funds and infrastructure is making solid waste
management services one of the most expensive services. Although municipali-
ties and councils have assigned fees for the collection and transferring of wastes,
few people have been able to pay for the services, and hence the revenue actually
collected from the fees has contributed to less than 20% of the money needed to
run the services (UNEP 2003; Khatib and Al-Khateeb 2009). According to
respondent localities the collection of management fees for factories’ generated
SW is performed in the mean of monthly fees (ranging from 10 to 100 NIS) as
stated by 81.3% of them. Other stated that they depend either on SW quantities
(12.5%) or on factory size (6.3% of respondents). On the other hand, the percent-
age of respondent localities that said the current solid waste management budget is
enough was 25%, and also 25% of them said sometimes it is enough, while 50% of
them said it is not enough.
Labors in SWM Sector

As a result of the above facts about SWM, the results of questions regarding labor
specialized in working in SWM section were as expected in terms of the following:
• There are no labors specialized in working in SWM.

• Labors in SWM section are always wearing protective clothes by 43.8%; labors in
SWM section are sometimes wearing protective clothes by 43.8%, labors in
SWM section are never wearing protective clothes by 12.5%.
• Inoculating against diseases like tetanus and typhoid: 37.5% confirmed it and
18.8% indicated partly inoculating labors; but in most of the cases (43.8%), there
is no inoculation.
• Labor awareness about the safety principles and how to deal with solid waste is
existent in 82.4% of the cases.
• The required training that suit their work: 11.8% confirmed that labors get the
required training, 52.9% that the labors get sometimes the required training, and
35.3% indicated the absence of the aforementioned activities.
• Safety and health regulations application imposed by specialized authorities: in
most cases (47.1%) this is frequent and in others (41.2%) occasional.
SWM Practices on Factory Level
ISW Generation
Development of proper industrial waste management system needs to know the
mean generation rate of ISW expressed as kg/day and m3/day; both of them are
necessary in order to determine the proper way of handling, for example, wastes such
as paper and cardboard, plastic, and wood have a high volume, so special collection
technology is necessary. This could take the form of mechanical volume reduction or
another processing technique. According to the results of this field research, there
were no machines to reduce volume of solid wastes.
Mean generation rates in this study were calculated depending on quantities of
ISW produced by factories. The results were estimations since they depend on the
estimates of the respondent from factories. The mean generation rates of ISW
produced from factories is presented in Fig. 2. They are ordered from highest to
lowest rate is 719.38 kg/day (262.6 tonne/year) from metals industries, 200 kg/day
(73 tonne/year) from paper and printing industries, 166.64 kg/day (60.8 tonne/year)
from food and beverage industries, 127.14 kg/day (46.4tonne/year) from plastic
industries, 39.4 kg/day (14.4 tonne/year) from chemicals industries, and 20 kg/day
(7.3 tonne/year) from textile industries.
In terms of quantities of ISW, Table 1 shows that metals, papers, plastic, and
plants are the most common wastes resulted in the survey; these wastes are generated
at 16, 14, 14, and 25 factories, respectively.
1000 719.38
Quantity of Industrial Solid Waste (kg/d)
200
127.14
100
64.8
47.4
29.8
24.64
20 18.4 20
10
1
plastics' food and chemicals' metals' textiles' papers'
beverages'
Industry Type
paper plastic metal textile plants chemicals
Fig. 2 Types and quantities of industrial waste per type of industry
Table 1 Mean and total generation rates of ISW

Average industrial solid waste kg/day Total ISW
Category Paper Plastic Metal Textile Plants Chemicals (kg/day)
Plastic 0.00 127.14 0.00 0.00 0.00 0.00 127.14
Food and 47.40 24.64 0.00 29.80 64.80 0.00 166.64
beverage
Chemicals 20.00 0.00 0.00 0.00 0.00 18.40 39.40
Metals 0.00 0.00 719.38 0.00 0.00 0.00 719.38
Textile 0.00 0.00 0.00 20.00 0.00 0.00 20.00
Paper 200.00 0.00 0.00 0.00 0.00 0.00 200.00
Total 267.40 151.78 719.38 49.80 64.80 18.40 1272.56
ISW Temporal Storage

Steel and plastic containers, which account for 36% for each of all temporal storage
facilities, are the commonest method of ISW storage, percentage of 14.6% represents
steel and plastic containers altogether. Other storage facilities are plastic sacks
(7.9%), steel containers and sacks (3.4%), and open to air (1.1%). Metallic con-
tainers of the same size as the plastic ones are used for ISW that has a relatively high
bulk density. In addition, containers which will carry high loads are made of metallic
materials. 66.3% of the containers do not have covers, but 33.7% do. A study by
Mbuligwe and Kaseva (2006) in Dar es Salaam city showed that solid waste storage
of open-air piles accounts for 43% of all storage facilities; other storage facilities are
metal and plastic bins (34%), open masonry enclosures (11%), 200 l used oil drums
(6%), covered masonry enclosures (4%), and concrete silos (2%).
Only 17% of the ownership of the containers is for factories and the other 83% is
for localities. The temporary storage of ISW in the factory vicinity is accounted for
96.6%, and 3.4% is out the factory vicinity.
ISW Collection and Transferring

94.4% declared that those responsible for collecting solid waste and transferring
ISW to temporary storage locations are the factory labors in general and specific
trained personnel/labors. The numbers of labors responsible for this activity are 1–2
labors (85.2%), 3–4 labors (9.1%), 5–6 labors (3.4%), and more than 6 labors
(2.3%).
ISW collection frequencies differ depending on generation rates, nature of the
waste, especially with respect to its biodegradability, and the transportation means
used. In 66.7% of the factories, the collection of ISW is performed once a day, 14.9%
twice a day, 14.9% three times a day or more, 3.4% once a week. The waste is
collected mechanically (57.5%) and manually (42.5%); manual handling is the most
common way to transfer ISW from inside factory to collection places. Figure 3
shows the percentages of means of transferring solid waste from inside factory to
collection places.
Local council vehicles and trucks that account for 52% constitute the highest
percentages of the means of transferring solid waste to the final disposal. The other
means and their percentages are presented in Fig. 4.
Treatment, Processing, and Final Disposal

Cleaning, separation, volume reduction, reuse, and others are the treatment methods
of ISW. Most of ISW is not treated prior of final disposal; 61 factories which account
for 69.3% do not treat SW after collection and before final disposal, 21 factories
which account for 23.9% always treat, and 6.8% sometimes treat. 83.33% of 21
Fig. 3 Means of transferring special qualified

solid waste from inside vehicles; 3; 3%
factory to collection places
musallic;
manual 21; 24%
handling and
manual
handcart; 3;
handling; 51;
4%
57%
handcart; 11;
12%
Fig. 4 Means of transferring rented

solid waste to the final vehicles or handcarts; 9;
disposal sites trucks; 7; 10% 13%
factory
vehicles or
trucks ; 17;
local council 25%
vehicles or
trucks; 35;
52%
factories recycle their waste and only 16.67% perform separation activities. 51.65%
of factories produce a mixture of process and nonprocess ISW but in small amounts,
the average rate of nonprocess ISW was 23.22 kg/day, while 48.35% of factories
produce process ISW only. A study by Mbuligwe and Kaseva (2006) in Dar es
Salaam city showed that 11% of the industries in Dar es Salaam city produce
significant quantities of nonprocess ISW, the other 89% of the industries produce
process ISW. Only 8.4% of factories in this study always separate process ISW from
nonprocess ISW, 14.5% sometimes separate ISW, and 77.1% do not separate ISW.
85.7% of factories do not separate their ISW into specific components, while
9.9% sometimes perform separation activities, and 4.4% always separate ISW into
specific components. In the case of providing the required containers, the respondent
had been asked if they were ready to separate ISW, the results were: 5% of
respondents are willing to separate ISW against paying, 75% are not interested to
paying but they are willing to separate, and 20% reported their indifference in the
aforementioned. The hazardous classification of SW produced by the factory
according to the respondents was: 12.2% classification of SW as low threat on
human and environment and 87.8% classification as no threat at all.
SW may constitute a resource (sold to other industries/factories as secondary raw
material), but unfortunately, 88.4% of respondents said that they do not sell ISW or
part of it and only 11.6% said they sell it to individuals. 29.2% of factories are paying
for disposing SW, while 70.8% do not pay at all. The main methods for final disposal
of ISW are as shown in Table 2.
94.4% of factories do not record the daily SW produced, and 93.3% of factories
do not have written instructions (guide manual) about dealing with ISW. There is a
lack in monitoring of SWM at the factory level, 5.7% of respondent factories said
that there are governmental authorities that follow up the issue of SWM, but 93.1%
of them declined the performance of this activity. 80.8% of respondents said these
authorities do not impose regulations regarding handling of SW produced, even
Table 2 Results of final Methods of final disposal Percent (%)

disposal methods of ISW
On-site treatment 1.1
in factory survey
Backfilling in special dumping sites 1.1
Backfilling in local council landfill 54.5
Random disposal 1.1
Burning outside factory 1.1
Burning inside factory 1.1
Reuse 4.5
Recycle 27.3
Transferring to unknown site 1.1
I do not know 6.8
Total 100.0
though 90.7% said there is a need to impose such regulations. Almost half of them
(47.4%) did not confirm the fact that these authorities impose penalties when
regulations do not apply. Overall, 75.9% of respondents were satisfied with the
service of transferring ISW to the final disposal.
Safety and Security of Factory Labors

The results of survey regarding safety and security of factory labors can be summa-
rized as:
• 86.4% of factories aware labors of safety and mechanism of dealing with SW.
• 74.2% of factories trained labors in accordance with their work nature and their
relation with SW.
• 79.8% of factories apply safety regulations and rules.
• 46% of factories said that labors wear special uniform to protect them while
collecting and transferring SW.
• 75.6% of factories do not have an accident guide manual to react during and after
accidents.
Cleaner Production Principles Application

The survey shows that 60 factories that accounted for 66.3% of factories adopt an
integrated preventive environment strategy; this result is considered high compared
to only 4 industries out of 170 which had plans to implement an Environmental
Management System in Asegra in Spain (Casares et al. 2005).
Outcomes of social survey conducted in eight West Bank districts made by
Khatib and Al-Khateeb (2009) showed that the level of knowledge concerning
reuse and recycle is poor; referring to outcomes of this study, 23.1% of respondent
heard about CPP; 31.6% of them from TV, 26.3% from internet, 10.5% from radio
and workshops, and 5.3% from bulletins.
The results of using raw materials were: 95.6% of factories use the raw materials
in their production process, while 4.4% of them use either reused or recyclable
materials. The respondents were asked if they were ready to use SW as raw materials
in their factories (if possible), 38.2% of them replied positively and 61.8% nega-
tively, but most of the latest belong to the food and beverages industry. 16.3% of
respondent can replace raw materials by others with lower SW production, while
83.7% cannot because the category of industry (food and beverages industries) for
example, lower prices of raw materials used, and sometimes no substitute for raw
materials.
Low percentages of industries reuse or recycle SW for use as raw materials in
their production processes; both intra- and inter-industry reuse and recycling are
practiced. It is found that 13.6% of factories reuse and 16.5% recycle ISW as intra-
industry reuse and recycle; which means SW are collected from generation points
and reused directly in industrial processes or recycled for eventual use within the
same industry. 77.3% of the recyclable materials are used as raw materials, and
22.7% of them used as an initial materials help in production.
Nevertheless, inter-industry reuse, which means SW discarded by one industry
are reused directly or processed for use as raw materials in another industry, is
practiced in recycling paper plant in Hadera (Al-Hudayrah) (occupied Palestinian
city in 1948) as mentioned by Eng. Abdulrahman Abu Ras; he said that there is no
economic feasibility to recycle papers at small scales; it depends on economies of
scale (Al-Qasrawi Industrial & Trading Co. L.T.D 2012).
Industrial Solid Waste Management Performance Indicators

Nine indicators were conducted in order to evaluate the performance of the factories
in SWM sector, and they also represent the main obstacles of the application of CPP.
Overall, respondents indicate that the situation of temporary storage inside the
factories is moderate (80.2%) since the internal management of the factories regard-
ing that issue had high percentages in terms of 95.3% said that number of containers
is enough, 94.4% of industries have no problem in storing inside factory, 80.7% said
there are no dogs or cats near SW containers; while 66.3% of the containers do not
have covers; the reason may be attributable to the nature of the waste produced by
the factories which means waste produced are not attractive to animals. Also 77.1%
do not separate process from nonprocess ISW and 85.7% of factories do not separate
their ISW into specific components; these percentages can be reduced significantly if
there are programs that encourage the application of CPP.
The outcomes of CTI research indicate that the situation of collection and transfer
ISW inside the factories is good (90.1%) even though 72.7% reported that there is no
monitoring for transferring and disposing of SW. The monitoring is responsibility of
ministries and institutions related to waste management that is supposed to impose
instructions in this regard and follow their implementation on the ground, and
impose real penalties when regulations not applied.
The outcomes of TFDI research indicate that the situation of treatment and final
disposal of ISW is good (81.3%). However, there are some negative practices such
that 69.3% of factories do not treat SW after collection and before final disposal. This
high ratio does not belong to the factories internal management alone, it belongs
significantly to governmental authorities and localities policies which do not support
or encourage treatment of SW. Maybe because even if all factories treat their wastes
(which means more efforts and costs), in the end the segregated wastes will come to
the same final disposal.
The outcomes of CPI research indicate that the situation of cleaner product of
ISW in general is good (97.8%). Only 23.1% of respondents had heard about CPP; a
result that is considered low compared to the result of 31.8% that resulted from a
survey conducted in Nablus and Ramallah and Al-Bireh governorates by Al-Khatib
et al. (2015). This can be overcome by disseminating CP concepts through multi-
media and campaigns in all Palestinian territories to increase awareness of all
relevant industrial and SWM sectors. 61.8% replied negatively when asked if they
were ready to use SW as raw materials in their factories; a reasonable answer for food
and beverage factories which constitute the highest percentage of the questioned
number of questionnaires (25 out of 91 questionnaires). The absence of an integrated
SWM system in this field (not involving recycle and reuse) is not creating the
background to apply internationally tested good practices.
The outcomes of Safety and Security Indexes (SSI) research evaluated the
situation as good (39.6%), as moderate (40.7%), and as bad (19.8%). High percent
of factories have good concern of labors in terms of safety and mechanism awareness
of dealing with ISW and trained labors in accordance with their work nature, since
79.8% apply safety regulations and rules. On the other hand, in 75.6% of factories
there is an accident guide manual to react during and after accidents when they occur.
The outcomes of the research indicate that all cleaner production obstacles
indicators are strong (over 80%), which indicated a significant weakness in the
application of cleaner production aspects on policy, financial, technical, and admin-
istrative levels. The aforementioned situation may be improved through the adoption
of SWM and CP roadmaps by the governmental authorities and of course the
imposition of supportive policies.
Conclusions and Recommendations
This chapter presented the final results of two parallel surveys (in localities and in
local factories) regarding the current SWM in Hebron governorate and the existing
opportunities for the application of cleaner production principles in the governorate.
The most notable deficiency of the existing ISW management practices in Hebron
governorate is that the hazardous component of the ISW is not segregated from the
rest of the waste for appropriate treatment. Additionally, the final disposal is
performed in dumpsites. This situation is expected to be improved when Al-Minya
sanitary landfill will start operating.
SWM on factories level is good in some aspects and need improvements in
other; for example, the status of collection and transferring of ISW inside the
factories and labors safe and security is good and has no pressing problems. On the
other hand, the reuse and recycle aspects are rather low; the results showed that only
21 out of 91 factories treat their wastes and this can be partly attributable to the
absence of supported policies from the responsible local/governmental authorities.
Regular monitoring and treatment of ISW are the first steps towards the identification
of needs and the application of improvements actions.
Involved actors in SWM sector must develop and update the legislative frame-
work that is expected to support an integrated SWM and encourage the reduction of
SW quantities, which are currently dumped/landfilled, by developing an incentives
system for factories backed-up with targeted projects in order to reduce and/or
promote recycling of ISW. A good coordination between the responsible authorities
and the factories will define responsibilities and enforce clear and viable policies. A
cost-benefit analysis to assess the feasibility of recyclable SW in existing landfills
versus separating and recycling SW items in new recycling plants will show them the
roadmap towards problem solving and transfer costs mitigation. Recording,
auditing, and continuous collection of data will act positively in order to update
the data of hazardous waste including types, quantities, sources, and impacts.
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Indoor Air Pollution Around Industrial
Areas and Its Effect: A Case Study 12
in Delhi City
Jitendra Kumar Nagar, Raj Kumar, J. P. Shrivastava, and

Geetanjali Kaushik
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
Suspended Particulate Matter and Respiratory Illnesses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
Selection of Study Areas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
Medical Examination of the Children (PFT/PEFR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
Statistical Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
General Profile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
Distribution Patterns of Indoor Suspended Particulate Matter (SPM) . . . . . . . . . . . . . . . . . . . . . . 311
Respiratory Illness in Children . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
Association of Asthma, Rhinitis, and URTI in Children with Indoor SPM . . . . . . . . . . . . . . . . 314
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
Abstract
Air pollution a global health problem is a significant issue in developing countries
particularly India. As per statistics, 30% of Delhi’s population suffers from
J. K. Nagar (*) · R. Kumar

Vallabhbhai Patel Chest Institute, University of Delhi, New Delhi, India
e-mail: jitendranagar79@gmail.com; rajkumarvpci@gmail.com
J. P. Shrivastava
Centre of Advanced Studies and Department of Geology, University of Delhi, New Delhi, India
e-mail: jpshrivastava.du@gmail.com
G. Kaushik
MGM’s Jawaharlal Nehru Engineering College, Mahatma Gandhi Mission,
Aurangabad, Maharahstra, India
e-mail: geetanjaliac@gmail.com

https://doi.org/10.1007/978-3-319-73645-7_158
304 J. K. Nagar et al.
respiratory disorders due to air pollution. Indoor air quality has more effects on
human health, chiefly due to large amount of time (87%) we spend indoors in
modern times. A comprehensive study was performed in two industrial areas
(Shahdara and Shahzada Bagh) of Delhi to assess the impact of indoor suspended
particulate matter (SPM) on respiratory diseases in children.
General physical examination and systemic examination with special refer-
ence to respiratory system was carried out by chest physician. Demographic
profile including house condition and environmental factors were collected with
the help of questionnaire. Spirometry was performed with the electronic portable
spirometer as per recommendations of the American Thoracic Society. Indoor
SPM level was measured by the Handy Air Sampler (Low Volume Sampler) with
1 LPM (liter per minute) flow rate. A total of 831 children (59.7% male and
40.3% female) were investigated in Shahdara and Shahzada Bagh industrial areas
of Delhi. The mean concentration level of indoor SPM was three times higher
than the CPCB standard and seven times higher than the WHO standards. 11.8%
children were diagnosed to have asthma of which 14.2% were in Shahdara and
9.6% in Shahzada Bagh. Children were also diagnosed to have rhinitis (38.9%)
and upper respiratory tract infection (36.2%) in the both study areas. The mean
level of indoor SPM was high in the houses where children had diagnosed to have
asthma, rhinitis, and URTI.
The present study concluded that the high concentration level of airborne
particulate matter was responsible for the increased number of respiratory dis-
eases such as asthma, rhinitis, and URTI in children. It was also concluded that
indoor air pollution and the housing location in industrial areas predisposed the
children to respiratory infections.
Keywords
Indoor air pollution · Particulate matter · Industrial area · Respiratory diseases
Introduction
Urban air pollution is a major global environmental health problem causing approx-
imately three million deaths per year in the world, as a result of exposure to
particulate matter (WHO 2001). Suspended particulate matter (SPM) has serious,
immediate, and long-term impact on human health and physical environment (Streit
and Guzman 1996). The adverse health effects of atmospheric particulate matter
were graphically illustrated by pollution episodes in Belgium’s industrial Meuse
Valley in 1930; Donora Pennsylvania, USA, in 1948; and London smog, England, in
1952 (NEPC 2001).
These particulate matters are also associated with increased respiratory symp-
toms, increased hospitalization for respiratory diseases, and increased cardiopulmo-
nary mortality (Bascom et al. 1996). Recent findings of Pandey et al. (2005) also
suggested that 30% of Delhi’s population suffers from respiratory disorders due to
air pollution and the incidence of respiratory diseases in the city is as high as
12 Indoor Air Pollution Around Industrial Areas and Its Effect: A Case. . . 305
12 times of the national average. In terms of SPM, Delhi is the fourth most polluted
city in the world (HEI 2002). Delhi’s annual average concentration of PM10
is highest among major Asian cities ranging between three and four times the
Indian standard in 2001–2004 (HEI 2002). Human beings are exposed to heavy
metals and other elements in airborne particulate matter, soils, water, and food, and
in other materials which come in contact with the man. Certain heavy metals often
occur in abundances, considerably above their background levels (US EPA 1982).
Anthropogenic processes in urban areas increase rates of mobilization of these
elements from their natural states (US EPA 1982). These increased concentrations
pose threat to the human health. Whether the immediate pathways to man
are directly from inhalation of polluted air, from ingestion, or by other means,
the overall sequence of transport links between the pollution sources of
heavy metals and a human receptor generally includes an atmospheric route as an
important part. Consequently, the measurement of heavy metal concentrations in
airborne suspended particulate matter is of global significance to human health
(US EPA 1982).
Indoor air quality has more effects on human health, chiefly due to large amount
of time we spend indoors in modern times. Jenkins et al. (1992) have observed that
urban people spend on an average 87% time in indoors and remaining 6% in
outdoors. Few persons – the old, the very young, and the children – spend all their
time indoors and are susceptible to the effects of pollutants. Women and children are
the most vulnerable as they spend more time indoors and are exposed to smoke.
Appraisal of indoor air quality is one of the most important aspects in understanding
the impact of particulate pollution on human health (Lee et al. 1997). Indoor SPM
concentrations depend on both indoor and outdoor sources and removal processes,
such as air exchange or chemical reactions (Phillip et al. 1993). The main sources of
indoor particulate matter are cooking, tobacco smoking, kerosene heating, wood
burning, resuspension of particles by people and pets, dusting and vacuuming,
showering, operation of humidifiers, electric motors, and transport from outdoors
via leakage through the walls, windows, or the ventilation system (Gulliver and
Briggs 2004; He et al. 2004). Resuspension of particles by human movement
contributed to the coarse mode of indoor particles (<1 μm size). Secondary particles
in the indoor environment are formed by gaseous pollutants through the process of
gas-to-particle conversion.
It is well established that indoor air is simply an extension of the ambient air
(Jones et al. 2000). Air penetrates indoors through doors, windows, and air condi-
tioners. Assuming that there is no source of pollutant in the indoor, the entering air
would be filtrated by whatever it passes through. In a humid or rainy day, outdoor
pollutants tend to be washed out, while, due to the relative constant humidity indoor,
the air quality is much worse even without any indoor activity (Jones et al. 2000).
Yocom (1982) pointed out that the indoor and outdoor relationships are complex due
to interactions of various factors such as meteorological, indoor sources and sinks
and pollutant depletions, filtrations, and ventilations. Lee et al. (1997) studied air
quality during the summer season in Korea, and their field measurements showed
that outdoor air contributed 50–100% of indoor pollution. Koponen et al. (2001)
studied effects of outdoor air pollution on indoor air with emphasis on the ventilation
system and found that indoor particles were mainly of outdoor origin and that the
ventilation had a strong influence on indoor particle characteristics and concentra-
tions. Moreover, indoors and outdoors airborne particulates differ in their types,
characteristics, concentrations, and sources (Jones et al. 2000).
Suspended Particulate Matter and Respiratory Illnesses
Epidemiological studies (Dockery et al. 1993; Bascom et al. 1996; McConnell et al.
2003) have established that the suspended particulate matter is associated with more
frequent respiratory allergy because airborne particulates easily reach the deepest
recesses of the lungs and damage. Particulates are especially harmful to people with
lung diseases such as asthma, bronchitis, rhinitis, and chronic obstructive pulmonary
disease. Exposure to particulate matter can trigger asthma attacks and cause cough,
wheezing, phlegm production, shortness of breath, common cold, throat congestion,
and respiratory irritation in individuals with sensitive airways (Bascom et al. 1996).
Zemp et al. (1999) in Switzerland found positive correlation between annual mean
concentrations of total suspended particulates and PM10 and chronic phlegm pro-
duction, chronic cough, breathlessness, wheezing, chest tightness, and current
asthma. Bronchitis was reported to be more prevalent among children with asthma
living in communities with high content of ambient PM10 (particulate mass less than
10 μm in diameter) in combination with high sulfur dioxide and sulfate particulate
matter (PM) in 24 cities of the eastern United States (Dockery and Pope 1994).
Environmental health effect studies conducted between 1990 and 2000 have shown
an association between exposure to particulate matter and increases in daily mortal-
ity and symptoms to certain illness in human beings (Dockery and Pope 1994).
Studies (US EPA Report 1997) indicated that tens of thousands of elderly people die
prematurely each year from exposure to fine particles and showed that exposure to
fine particles was associated with hospital admissions each year.
Asthma is a chronic respiratory disease characterized by sudden attacks of
labored breathing, chest tightness, and coughing. It is a complex multifactorial
disease resulting from an interaction between individual genetic susceptibility and
exposure to various environmental factors. The prevalence of asthma has increased
worldwide both in the developed and developing countries during the past two or
three decades (Magnus and Jaakkola 1997), and the increase appears to be greatest
in children, teenagers, and young adults (Burney et al. 1996). There is substantial
epidemiological evidence indicating a link between asthma morbidity including
deterioration in lung functions, emergency department visits, and hospital admis-
sions with the exposure of high concentration of suspended particulate matter (WHO
Report 1987). Galan et al. (2003) studied the short-term effects of air pollution on
daily asthma emergency room admissions in Madrid, Spain, and found the associ-
ation between air pollutants and increase in asthma emergency room admissions. A
study based on the air pollution and asthma admission among children has been
carried out in Hong Kong, China, and found that the ambient levels of PM10 and
NO2 was associated with childhood asthma hospital admissions but SO2 was not
associated with hospital admissions among children (Lee et al. 2006).
Allergic rhinitis has increased worldwide in the last few decades, possibly to a
greater extent than asthma (Howarth and Holmberg 1995). An epidemiological study
(Miyamoto 1997) in Japan demonstrated the effects of air pollution, with increased
coughing, sputum production, wheezing, throat irritation, asthma, and allergic rhi-
nitis. The incidence of allergic rhinitis and asthma has been shown to be greater in
areas where there is heavy traffic and hence high levels of automobile exhaust
emissions. An association between air pollutants and daily consultation with general
practitioners for allergic rhinitis has been investigated in London, United Kingdom
(Hajat et al. 2001). The mean level of air pollutants, SO2, NO2, and PM10, were
significantly associated with the increase in the number of consultations for allergic
rhinitis (4.8% in children and 15.3% in adults). Exposure to indoor air pollution,
especially to particulate matter, from the combustion of biofuels (wood, charcoal,
agriculture residues, and dung) has implicated as a causal agent for acute respiratory
diseases in the developing countries (Ellegard 1996; Kumar et al. 2005). The effects
of indoor air pollution from biomass combustion on acute respiratory infections in
developing countries have been determined by Ezzati and Kammen (2001) and
found that acute respiratory infections and acute lower respiratory infection were
increasing with average daily exposure to PM10. Acute respiratory infections (ARI)
constitute to more than 6% of the global burden of diseases and mortality, mostly in
developing countries (WHO Report 1999). Acute lower respiratory infections
(ALRI) led to mortality from infectious diseases, with an estimated 3.5–4.0 million
deaths worldwide between years 1997 and 1999 (WHO Report 1999, 2000).
ARI accounts for 15–30% of childhood death, with a mortality ranging from 3.2
to 13.8 deaths/1000 children. Bronchiolitis, acute laryngitis, and pneumonia are
primarily responsible for the majority of ALRI-related deaths among children
(Sharma et al. 1998).
Sharma et al. (1998) conducted a prospective study in two urban colonies of Delhi
and studied infants to determine the incidence of acute lower respiratory infection
(ALRI) and its relationship to indoor air pollution due to fuel used for cooking (wood
or kerosene). In this study, pneumonia was the most common ailment in the infants.
Bronchiolitis was reported in 22.5% of the wood group and 27.1% of the kerosene
group. A higher incidence of ALRI was reported in kerosene users. Several studies
based on indoor and outdoor air pollution were undertaken in different countries
(Dockery et al. 1993; Bascom et al. 1996; Horak et al. 2002; Quiterio et al. 2004).
But, most of the studies are based on outdoor air pollution and respiratory illness in
adults or children. In India, studies on indoor suspended particulate matter in the
industrial areas of metros and its relationship with respiratory diseases (in children)
are lacking.
Present work is aimed at studying indoor suspended particulate matter (SPM) and
its effects on the respiratory allergy in children (7–15 years age), living in close
vicinity of the industrial areas of Delhi.
Materials and Methods
Selection of Study Areas
The Central Pollution Control Board a premier Indian agency for pollution moni-
toring and control has identified the Shahdara and Shahzada Bagh as industrial areas
of Delhi based on the presence of industrial units and high pollution level. Shahdara
and Shahzada Bagh are well-recognized industrial areas of Delhi and having more
than thousand industrial units. These localities are better for the study of the
exposure of indoor air pollution and its impact on human health in the industrial
areas of metros. So, Shahdara and Shahzada Bagh for the present study were
selected.
Shahdara is located in the northeastern part of Delhi (Fig. 1). The surrounding
area is open and flat with dense residential localities at Dilshad Garden and Nand
Nagri and densely located small-scale industrial units at Jhilmil industrial estate.
Dense residential localities of Vivek Vihar and Jhilmil area are located toward
southwest of the study area. There are a number of industrial units located in
Fig. 1 Showing (a) index map and (b) map of Delhi, where Shahzada Bagh and Shahdara
industrial areas are located
Shahdara industrial area, Loni Road and Vishwas Nagar comprising industrial units
of steel industries, chemical units, pickling units, copper wire drawing units, plastic
units, engineering units, and other small-scale industries. A few battery manufactur-
ing units are also located in Shahdara industrial area. All three socioeconomic
classes, i.e., lower, middle, and upper, are presented in the area. The study area in
Shahdara is situated near industries, railway station, metro-railway station, slums,
traffic roads, petrol pumps, hospitals, and drains.
Shahzada Bagh is located in the northwest part of Delhi (Fig.1). The surrounding
area is open, with flat plateau consisting of a large number of industries in the west
and southwest, including Lawrence road industrial area, Moti Nagar industrial area,
DLF industrial area, and Kirti Nagar industrial area comprising large-scale industrial
units of steel industries, metal-based industries, and chemical plants. There are about
600–700 small iron-based industries using liquid fuel in Wazirpur industrial area. In
extreme south, a large number (about 2000) of pickling and electroplating units are
located in Anand Parbat industrial area. A few stone crushers had also been situated,
and these were in operation till June 1992 at Anand Parbat area contributing
atmospheric particulate load, but presently these are not in operation.
Both the study sites are divided into three socioeconomic colonies based on their
economic status, each one representing the lower (poor people having less than 3000
rupees monthly income and living in a house with one room or Jhuggi-Jhopari),
middle (the peoples having 5000–10,000 rupees monthly income and living in a house
with two to three rooms), and upper class (rich peoples having more than 20,000
rupees monthly income and living in a big house with four to five rooms). Hundred
houses with children aged 7–15 years from each socioeconomic class were selected
for the present investigations including their health checkup, and 25% houses of these
houses were selected for monitoring of indoor suspended particulate matter.
Sampling
Sampling of the indoor suspended particulate matter was done by Handy Air
Sampler APM 810 with a flow rate of 1 LPM (liter per minute) and a glass fiber
filters (Whatman GF/A, 2.5 cm diameter). This instrument was installed for 6 h
sampling period (10.00 a.m. to 4.00 p.m.) in the center or corner of the room, with
the inlet roughly 1 m above the ground level, corresponding with the breathing
height of the children.
Medical Examination of the Children (PFT/PEFR)
A list of all the members with 7–15 years of age was obtained. The questionnaire
for health history of child was administered at the house itself. The detailed
questionnaire was developed, based on works of the American Thoracic Society
(Ferris 1978), the British Medical Research Council (BMRC 1960), and the Inter-
national Study of Asthma and Allergies in Childhood (Keil et al. 1996). Data
regarding the symptoms including cough, phlegm production, shortness of breath,

wheezing, common cold, and throat congestion were collected using this question-
naire. It also contained questions about a history of smoking in the family, type of
cooking fuel used, ventilation at the cooking place, and occupancy per room.
Examination of the child including pulmonary function test was done at home. If
they were not present in the house, a special medical camp was also organized in
nearby area where examination and other tests were done under the supervision of
medical doctors. Health examination of the children and their pulmonary function
test were carried out by a team of chest physician from Vallabhbhai Patel Chest
Institute, University of Delhi, India.
Pulmonary function test (PFT) was carried out using an electronic portable spirom-
eter (Spirobank, Medical International Research, Roma, Italy). The equipment was
calibrated daily before the tests. The tests were carried out in the sitting position with
the noseclip applied. Maximal expiratory flow volume (MEFV) curves were obtained as
per the American Thoracic Society recommendations (ATS 1995). Three acceptable and
at least two reproducible curves were obtained in each subject. The highest values of
forced vital capacity (FVC) and force expiratory volume (FEV1) were selected,
irrespective of the curves came from flow rates was obtained from the “Best Curve,”
i.e., the curve with the highest sum of FVC and FEV1. Some of the subjects were unable
to cooperate and perform the spirometry maneuvers satisfactorily. In these, peak
expiratory flow rates (PEFR) were obtained with a Wright’s peak flow meter (Wright
Peak Flow Meter, Spanish International Pharmaceutical Company, Spain). The highest
of the three recordings was noted. Airway obstruction was documented when PEFR was
less than 20% predicted values for that age and sex, and spirometry was done when
FEV1, FVC, or FEV1/FVC was <80% of predicted value.
Asthma, rhinitis, and respiratory tract infection (URTI) were examined based on
the presence of airway obstruction and history of respiratory symptoms (cough,
phlegm production, shortness of breath, wheezing, common cold, throat congestion)
in children. The asthma was diagnosed by the guidelines of the American Thoracic
Society (Ferris 1978), the British Medical Research Council (BMRC 1960), and the
International Study of Asthma and Allergies in Childhood (Keil et al. 1996). The
diagnosis of rhinitis was made if the children were having at least two of the
following symptoms for over 2 years – blocked nose, running nose, itch nose, and
sneezing (Adamopoulos et al. 1995). Diagnosis of upper respiratory tract infection
(URTI) was made on the basis of the study conducted by Yamaya et al. (1998).
Statistical Analysis
The statistical analysis was performed on SPSS statistical software (SPSS Inc,
Chicago, IL version). The groups were compared for all variables using the “student
t-test” to compare equality for means and the “chi-square test” to compare category
value. The differences were considered to be statistically significant at the p < 0.05
(two tailed test) or 5% level of significance (Grover and Kumar 2008). Results so
obtained are presented in percentage and mean SD.
General Profile
During the present study, a total of 2122 houses were surveyed in Shahdara and
Shahzada Bagh industrial areas of Delhi. Children between 7 and 15 years were
present in 1103 houses, but family member allowed for study in only 647 houses
(Table 1). A total of 831children (59.7% male and 40.3% female) were studied in
Shahdara and Shahzada Bagh industrial areas. A group of 33.8% children were
found to be exposed by environmental tobacco smoke (ETS) or passive smoking,
whereas 70.3% of children’s family was using LP gas for cooking; however, 29.7%
of children’s family mainly from lower class was using biomass fuels (kerosene,
wood, coal, and cow dung cakes) for cooking. Families from upper and middle
classes had separate kitchen with exhaust, and lower-class families cooked in their
sleeping room as poor families lived in a single room. 45.1% families were aware
about indoor air pollution. Children showed respiratory symptoms including cough,
phlegm production, breathlessness, and wheezing and were diagnosed with respira-
tory diseases such asthma, rhinitis, and upper respiratory tract infection.
Distribution Patterns of Indoor Suspended Particulate Matter (SPM)
Indoor suspended particulate matter (SPM) was measured in the industrial areas
(Shahdara and Shahzada Bagh) of Delhi. The mean concentration level of
indoor SPM was 1049.7 452.4 μg/m3 (260–2380 μg/m3) in Shahdara and
1108.7 509.8 μg/m3 (310–2420 μg/m3) in Shahzada Bagh (Table 2). The
indoor SPM of Shahdara and Shahzada Bagh mainly distributed between 500 and
1500 μg/m3 (Fig. 2). The SPM level was very high in Shahdara and Shahzada Bagh
Table 1 Details of houses surveyed

House Children found in Houses allowed for Children
Study area surveyed houses study examined
Shahdara 1467 640 (43.63%) 319 (21.8%) 394 (11.4%)
Shahzada 655 463 (70.69%) 328 (50.1%) 437 (12.6%)
Bagh
Total 2122 1103 (51.97%) 647 (30.49%) N = 831
Table 2 Concentration of the indoor suspended particulate matter

Concentration of indoor SPM (μg/m3)
Study areas Houses (N) Minimum Maximum MeanSD
Shahdara 103 260 2380 1049.7 452.4
Shahzada Bagh 109 310 2420 1108.7 509.8
Total 212 260 2420 1080.0 482.4
2500
(b)
2000
Indoor SPM (μg/m3)
1500
1000
500
0
2500
(a)
2000
Indoor SPM (μg/m3)
1500
1000
500
0
0 40 80
Number of Houses
Fig. 2 Distribution of indoor SPM at (a) Shahdara and (b) Shahzada Bagh Industrial areas.
Abbreviations: + suspended particulate matter, μg microgram
areas, and it was approximately three times higher than annual standard for industrial
areas that was set up by the Central Pollution Control Board (CPCB) and seven times
higher than the WHO standards. High concentration of SPM was mainly due to the
presence of a large amount of industrial establishment and high density of road
traffic in these areas. Large-scale construction activities such as metro-rail, roads,
flyovers, and buildings may be also responsible for the high concentration level of
particulate matter in Delhi. Cooking and smoking also play an important role to
increase indoor SPM concentration in the houses, because cooking smoke and
environmental tobacco smoke are the main sources of indoor particulate matter. In
both the areas, indoor SPM concentration was very high and most of the children
showing respiratory symptoms and suffering from respiratory diseases. It may be
possible that children are affected by high concentration of SPM; therefore it is

necessary to understand the relationship between respiratory diseases and SPM.
Respiratory Illness in Children
Children had history of cough (61.5%), phlegm production (32.2%), shortness of

breath (27.7%), and wheezing (16.9%) in Shahdara and Shahzada Bagh industrial
areas of Delhi (Table 3). Ninety-eight (11.8%) children were diagnosed to have
asthma of which 14.2% were in Shahdara and 9.6% in Shahzada Bagh. Asthmatic
children were in lower class (7.9%), middle class (15.7%), and upper (11.9%) class
(Table 4). 38.9% children were diagnosed to have rhinitis of which 44.4% were in
Shahdara and 34.1% in Shahzada Bagh. Rhinitic children were in lower (31.9%),
middle (48.9%), and upper (36.6%) class (Table 4). 36.2% children were diagnosed
to have upper respiratory tract infection of which 43.1% were in Shahdara and
Table 3 History of respiratory symptoms in children

Socioeconomic classes
History of respiratory Study Lower Middle Upper Total
symptoms areas (n = 279) (n = 268) (n = 284) (n = 831)
Cough Shahdara 78 (60.5%) 90 (69.8%) 79 (58.1%) 247 (62.7%)
Shahzada 92 (61.3%) 88 (63.3%) 84 (56.8%) 264 (60.4%)
Bagh
Phlegm production Shahdara 23 (17.8%) 45 (34.9%) 28 (20.6%) 96 (24.4%)
Shahzada 53 (35.3%) 58 (41.7%) 61 (41.2%) 172 (39.4%)
Bagh
Shortness of breath Shahdara 43 (33.3%) 47 (36.4%) 36 (26.5%) 126 (32.0%)
Shahzada 27 (18.0%) 39 (28.1%) 38 (25.7%) 104 (23.8%)
Bagh
Wheezing Shahdara 34 (26.4%) 35 (27.1%) 32 (23.5%) 101 (25.6%)
Shahzada 7 (4.7%) 20 (14.4%) 13 (8.8%) 40 (9.2%)
Bagh
Table 4 Asthma, rhinitis, and upper respiratory tract infection (URTI) in children
Socioeconomic classes
History of Study Lower Middle Upper Total
respiratory diseases areas (n = 279) (n = 268) (n = 284) (n = 831)
Asthma Shahdara 15 (11.6%) 22 (17.1%) 19 (14.0%) 56 (14.2%)
Shahzada 7 (4.7%) 20 (14.4%) 15 (10.1%) 42 (9.6%)
Bagh
Rhinitis Shahdara 49 (38.0%) 73 (56.6%) 53 (39.0%) 175 (44.4%)
Shahzada 40 (26.7%) 58 (41.7%) 51 (34.5%) 149 (34.1%)
Bagh
URTI Shahdara 47 (36.4%) 71 (55.0%) 52 (38.2%) 170 (43.1%)
Shahzada 36 (24.0%) 49 (35.3%) 46 (31.1%) 131 (30.0%)
Bagh
30.0% in Shahzada Bagh. Children with upper respiratory tract infection were in
lower (29.7%), middle (44.8%), and upper (34.5%) class (Table 4). A number of
children suffering from asthma, rhinitis, and upper respiratory tract infection were
more in middle class compared to lower and upper socioeconomic classes, because
middle class of Shahdara and Shahzada Bagh was situated near the polluted indus-
tries and traffic roads. On spirometry examination, 69 (8.3%) children had airway
obstruction of which 11.2% in Shahdara and 5.7% in Shahzada Bagh.
Association of Asthma, Rhinitis, and URTI in Children

with Indoor SPM
In the present study, correlation between respiratory diseases and indoor SPM was
performed using SPSS and student t-test of 5% significant level. The mean level of
indoor SPM was significantly ( p = 0.005) high in the houses of Shahdara where
children were diagnosed to have asthma. It was also high in Shahzada Bagh where
children had asthma but not statistically significant ( p = 0.107) as per the details
given in Table 5. There are few studies (Galan et al. 2003; Morand et al. 2005)
carried out in western countries that supports the present study and established
association between asthma and air pollutants. A cross-sectional epidemiologic
study carried out in six French cities found the association between long-term
exposure to air pollution and asthma (Morand et al. 2005). Total 5.3% school
children have prevalence of asthma, of which 6.9% was in boys and 3.8% was in
girls. Averaged concentrations of particulate matter (PM10), sulfur dioxide (SO2),
and nitrogen dioxide (NO2) were calculated at children’s schools. Asthma was found
to be positively related to an increase in the exposure to PM10 and SO2, but there is
no consistent positive association between NO2 and asthma. Analysis of the epide-
miologic literature demonstrated that prevalence of respiratory symptoms might be
higher in polluted areas, when industrial pollution was still important.
Allergic rhinitis in children has become a major public health problem in devel-
oped and developing countries (Lundback 1998). Fewer disputes are involved in the
clinical diagnosis of seasonal allergic rhinitis, the symptoms and seasonality of
which are characteristic and have been well established for many years. The major
symptoms of allergic rhinitis are sneezing; a clear, watery rhinorrhea; itching
Table 5 Correlation between asthma in children and indoor SPM

Study areas Asthma in children Mean SD of SPM (μg/m3) P value
Shahdara (n = 103) YES 12 1380.8 362.7 0.005*
NO 91 1006.0 446.4
Shahzada Bagh (n = 109) YES 10 1336.0 423.0 0.107
NO 99 1085.8 513.7
Total (n = 212) YES 22 1360.5 382.3 0.002*
NO 190 1047.6 483.0
Abbreviation: *Statistically significant
affecting the nose, eyes, and plate; and nasal obstruction (Parikh and Scadding
1997). Several epidemiological studies (Giccone et al. 1998; De et al. 2002; Morand
et al. 2005) have investigated the association between exposure to air pollutants and
respiratory allergy and found increased prevalence of allergic diseases with air
pollutants in well-developed countries. Preliminary studies from Germany and
Italy have suggested a positive correlation between traffic density and the morbidity
of allergic rhinitis (Giccone et al. 1998). Ambient air pollution level was also noted
and associated with the prevalence and severity of allergic rhinitis (De et al. 2002).
An association between air pollutants and daily consultation with general practi-
tioners for allergic rhinitis was investigated in London (Hajat et al. 2001). The mean
level of air pollutants, SO2, NO2, and PM10, were significantly associated with
increase in the number of consultation for allergic rhinitis and suggested that air
pollution worsens allergic rhinitis symptoms because these findings are consistent
with an acute effect of air pollution, particularly sulfur dioxide, particulate matter on
allergic rhinitis in both children and adults. In the present study, the mean concen-
tration level of indoor SPM was high in the houses of Shahdara ( p = 0.785) and
Shahzada Bagh ( p = 0.078) where children were diagnosed to have rhinitis, but it
was not statistically significant (Table 6).
Upper respiratory tract infection (URTI) was also positively correlated with mean
level of indoor SPM, because the mean concentration level of indoor SPM was high
in the houses of Shahdara ( p = 0.650) and Shahzada Bagh ( p = 0.059) where
children were diagnosed to have URTI but it was not significant (Table 7). Acute
respiratory infection (ARI), together with malnutrition and diarrheal disease, con-
stitutes the most common cause of illness and death among children in developing
countries. The incidence of ARI is considerably higher in developing countries;
Table 6 Correlation between rhinitis in children and indoor SPM

Study areas Rhinitis in children Mean SD of SPM (μg/m3) P value
Shahdara (n = 103) YES 44 1063.4 388.1 0.785
NO 59 1039.5 497.9
NO 75 1054.4 531.5
Total (n = 212) YES 78 1135.4 417.6 0.179
NO 134 1047.8 515.1
Table 7 Correlation between URTI in children and indoor SPM

Study areas URTI in children Mean SD of SPM (μg/m3) P value
Shahdara (n = 103) YES 43 1072.8 387.7 0.650
NO 60 1033.2 496.1
NO 78 1053.5 522.0
Total (n = 212) YES 74 1146.1 423.3 0.124
NO 138 1044.6 509.2
15–20% of children suffer from respiratory infection every year (Ministry of Health
and Family Welfare report 1992). Exposure to indoor air pollution, especially to
particulate matter, from the combustion of biofuels (wood, charcoal, agricultural
residues, and dung) has been implicated as casual agents of respiratory infection
(Ellegard 1996 and Sharma et al. 1998). A study (Ezzati and Kammen 2001) in
Kenya found the association between ARI and daily exposure of PM10 with the rate
of exposure above approximately 1000–2000 μg/m3. A time series study (Smith
et al. 2000) in Sao Paulo found stronger association of air pollutants and ARI.
The present study and other studies show that high concentration of particulate
matter may be responsible to cause asthma, rhinitis, and URTI in children and it may
be an environmental factor to cause respiratory disorder in human beings.
Conclusion
In 647 houses, a total of 831 children (59.7% male and 40.3% female) were
investigated in Shahdara and Shahzada Bagh industrial areas of Delhi. About 1/3
in each study area has family history of smoking. About 70% children’s family
member mainly from upper and middle class were using LP gas fuel for cooking, and
30% mainly from lower class were using biomass fuel such as coal, woods,
kerosene, and cow dung cakes for cooking. The mean concentration level of indoor
SPM was 1049.7452.4 μg/m3 in Shahdara and 1108.7509.8 μg/m3 in Shahzada
Bagh. The mean level concentration of indoor SPM was very high in Shahdara and
Shahzada Bagh industrial areas, and it was approximately three times higher than the
standard values with respect to industrial areas setup by the Central Pollution
Control Board (CPCB) and seven times higher than the WHO standards. High
concentration of SPM was mainly due to the presence of a large amount of industrial
establishment and high density of road traffic in these areas Children had history of
cough (61.5%), phlegm production (32.2%), shortness of breath (27.7%), and
wheezing (16.9%). Children diagnosed to have asthma (11.8%), rhinitis (38.9%),
and upper respiratory tract infection (29.7%). Children who are exposed to passive
smoking or environmental tobacco smoke (ETS) have more rhinitis and upper
respiratory tract infection. Asthma in children was significantly associated with
indoor SPM. The mean level of indoor SPM was high in the houses of Shahdara
and Shahzada Bagh where children had diagnosed to have asthma, rhinitis, and
upper respiratory tract infection.
The present study concluded that the high concentration level of airborne partic-
ulate matter is responsible for the increased number of respiratory diseases such as
asthma, rhinitis, and upper respiratory tract infection in children, because airborne
particulates easily reach the deepest recesses of the lungs and damage the respiratory
system of human beings. The high concentration level of indoor SPM increased due
to the presence of more than thousands of industrial units, power plants, construction
activities, vehicular traffic, municipal waste, and indoor sources like cooking fuels
and smoking.
Cross-References
▶ Air Quality Status and Management in Tier II and III Indian Cities: A Case Study
of Aurangabad City, Maharashtra
Study of Delhi City
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Scenario of Landfilling in India: Problems,
Challenges, and Recommendations 13
Swati, Indu Shekhar Thakur, Virendra Kumar Vijay, and Pooja Ghosh
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
Problems and Issues Related to Landfills . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
Leachate: A Toxic Soup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Toxic Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
Greenhouse Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
Others . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
Case Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
Recommendations to Solve Landfill Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
Build New Sanitary Landfill . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
Waste to Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Abstract
Landfilling is one of the major municipal solid waste (MSW) disposal methods
practiced worldwide. Though it is considered most cost-effective means of waste
disposal, but poor management practices specially in developing countries like
India are the major causes of environmental pollution. Recently several studies
have been carried out to understand the effects of landfill pollution on human
health as well on the environment. Toxic gas emissions from landfills pose a
serious threat to the environment as well as on human health. Some studies have
Swati · I. S. Thakur
School of Environmental Sciences, Jawaharlal Nehru University, New Delhi, India
e-mail: swati.wanwari@gmail.com; isthakur@hotmail.com
V. K. Vijay · P. Ghosh (*)
Centre for Rural Development and Technology, Indian Institute of Technology, New Delhi, India
e-mail: vkvijay@rdat.iitd.ac.in; pooja.ghosh9@gmail.com

https://doi.org/10.1007/978-3-319-73645-7_167
322 Swati et al.
shown that toxic gases released from landfill sites are even responsible for lung
and heart diseases in humans. Landfills also generate a toxic soup known
as leachate, formed when waste is subjected to biological and physiochemical
transformation. Leachate is highly toxic and causes land and groundwater pollu-
tion. This chapter aims to address the problems, both environmental and toxico-
logical, associated with the landfills, the challenges faced in the current scenario,
and the possible measures that can be taken to deal with the problem of municipal
solid waste management successfully.
Keywords
Municipal solid waste · Landfill · Leachate · Greenhouse gases
Introduction
The solid waste generation is increasing day by day due to rapid urbanization and
industrialization, and hence its management is becoming a great issue. Landfilling is
one of the most economical disposal methods that is used worldwide. Landfills can be
classified as open dumps, controlled dumps, and sanitary landfills (UNEP-IETC 1999).
Most of the solid waste management practice which is in use in developing countries
lies somewhere between open dumps and control dumps as there is no need of specific
equipment and expertise for dumping waste in open dumpsite (Daskalopoulos et al.
1998). These sites pose a great risk to environment and the human health. Open dump
sites have caught great attention of researchers who described its possible effects which
led to the closure of such sites in many of the developing countries. The generated waste
is disposed off in the landfills whether they are residual materials from materials
recovery facilities, residential waste, residue of the combustion of solid waste, industrial
waste, or hospital waste. The improper segregation, or complete absence of segregation
facility at the waste generation site, causes the accumulation of toxic waste mixture in
landfills. Toxic waste mixture contains PCBs, PAHs, pesticides, insecticides, etc. The
disposal of these toxic chemicals not only leads to the exposure of rag pickers to these
chemicals but also causes soil and groundwater pollution.
The landfills are meant for reducing the exposure of humans and environment
from toxic waste (Narayana 2009). But due to their unengineered nature, Indian
landfill sites are posing a threat to environment. The crude landfill sites prevail in
Indian scenario that lack baseliners, gas ventilation system, and leachate treatment
ponds. This results in environmental hazards and ecological imbalances due to
dumping of unsegregated waste from industries, hospitals, and houses on open
land (Narayana 2009). The excessive rain water percolation through the different
layers of landfill generates a contaminant laden liquid called leachate. The leachate is
the primary cause of mobilization of waste from landfill site to the surrounding
environment (Christensen and Kjeldsen 1989). However, a modern sanitary landfill
facility of waste disposal that contains baseliners, leachate, and gas collection system
is environmentally safe.
13 Scenario of Landfilling in India: Problems, Challenges, and Recommendations 323
The crude landfills have become a threat to human population due to the emission
of toxic waste in the surroundings and hence are under scrutiny. All the three
medium matrixes of the human exposure associated with landfills, i.e., air, water,
and soil, need to be critically evaluated, and thorough risk analysis needs to be done
for future safety measures. The various studies done on landfill leachate composition
showed the presence of organic pollutants from both biogenic and xenobiotic origins
(Christensen et al. 1992; Ghosh et al. 2015). Methanogenic decomposition in landfills
leads to the production of gases which primarily includes methane and carbon dioxide
(up to 90%) along with carbon monoxide (CO), nitrogen (N2), etc. The methane
released from landfills has a great global warming potential which is 23 times greater
than that of same amount of carbon dioxide (EIA 2003). Other toxic and polluting
substances present in landfills belong to the category of alcohols, hydrocarbons,
organosulfur compounds, and heavy metals (El-Fadel et al. 1997). Hence, leachate,
landfill gas, and toxic substances present in landfills are some of the major problems
related to landfills which can harm human and natural systems (Abbas et al. 2009;
Adeyemi et al. 2006; Akinbile and Yusoff 2011; Alekhya et al. 2013; Aljaradin and
Persson 2012; James 1977; Kangsepp and Mathiasson 2009; Lou et al. 2009;
Mor et al. 2006; Nagarajan et al. 2012a; Olsson et al. 2009; Smahi et al. 2013).
In India, about 91.4% of the collected waste was landfilled, and remaining 8.6%
was either incinerated (6.4%) or composted (2.2%) (Liu 2008). Sanitary landfills or
engineered landfills have the system installed for landfill biogas and leachate
collection and its treatment, but still there is a scope of improvement in the presently
used techniques to deal with landfill problems (Christian et al. 2003). Some
conventional leachate treatment method includes coagulation, flocculation, air strip-
ping, and settling which are costly in terms of equipment required, frequent chemical
usage, and energy requirement. Some pollution transfer technologies were also
used to treat leachate such as reverse osmosis and active carbon adsorption which
do not solve the environmental problem. In recent years, advanced oxidation pro-
cesses (AOPs) were proved to be an effective way for mineralization of recalcitrant
compounds present in leachate. However, it is quite expensive to treat leachate
in large scale via this technique. AOPs along with biological treatment processes
can be a possible effective and economical way of treating leachate (Wiszniowski
et al. 2006). Nitrification/denitrification is the most efficient and cheapest biological
process to remove nitrogen from leachate, but sometimes it is hampered by the
presence of toxic substances such as PAH-polyaromatic hydrocarbons, PCB-
polychlorinated biphenyls, AOX-absorbable organic halogens, humic acid, and
surfactant. So the novel composite technique which can utilize the positives of
each can be proved beneficial for current scenario of leachate treatment problem.
Several studies have reported that the exposure to toxic chemicals present
in dumping sites such as dioxins and heavy metals can cause human health
problems such as impairment of lung function and dermatological and
neurobehavioral problems (Agusa et al. 2003; Gelberg 1997; Minh et al. 2003,
2006; Nduka et al. 2013; Poulsen et al. 1995; Ray et al. 2005; Vrijheid 2000;
Zakaria et al. 2005). To assess the toxicological effects of leachate, chemical
324 Swati et al.
analysis of the sample is not sufficient. So it is aided by the use of various bioassays.
The report on bioassays used for leachate toxicity assessment has been recently
reviewed by Ghosh et al. (2017). They reported the use of battery of bioassays
for proper toxicological study which includes organisms from different trophic
levels. The present review seeks to gather the information on current problems
related to landfilling in India and its possible solution.
Problems and Issues Related to Landfills
Waste generation has tremendously increased in the past decade and has reached
62 million tonnes each year in India (Kumar et al. 2017). Former environment
minister, Shri Prakash Javadekar, pointed out that, out of 62 million tonnes of
waste, only 43 million tonnes are collected annually and only 28% of it was treated.
The rest was dumped in landfills. Current rate of garbage dumping leads to the
requirement of 1,240 ha of land as landfill per year. It is estimated that, by 2030, the
waste generation will increase to 165 million tonnes and will require landfill area
equal to the size of Bengaluru. If the improper treatment of waste and dumping
persists, soon the whole country will be under the muck. The landfill area in different
cities of India has been shown in Fig. 1.
Delhi, Mumbai, Chennai, Hyderabad, and Kolkata are the five highest solid
waste generating cities in India. The diverse form of waste is generated in different
cities which can be categorized in four major types such as hazardous waste, plastic
waste, e-Waste, and biomedical waste. The proportion of each is shown in Fig. 2.
Landfill area (hectares)

Guwahati
Chandigarh
Raipur
Kolkata
Ranchi Srinagar
Thiruvananthap Jaipur
uram Delhi
Ahmedabad Greater
Greater Mumbai
Hyderabad
Chennai
Greater
Bengaluru
Fig. 1 Area of landfills in different cities of India. (Source: CPCB)

Fig. 2 Classification and 9
Millions tonnes of waste per

amount of waste generated in 8
India. (Source: CPCB) 7
6
5
year
4
3
2
1
0
Hazardous Plastic e-Waste Biomedical
Type of waste
Initially the landfill contains large amount of biodegradable organic matter which is
subjected to anaerobic fermentation which leads to the formation of volatile fatty
acids (VFA) (Welander et al. 1997). The high moisture content aids the acid
fermentation, and hence this phase is called as acidogenic phase. At this phase,
95% of the organic matter consists of free volatile fatty acids (Wang et al. 2003;
Harsem 1983). Mature landfills are dominated by methanogenic microorganisms
which convert VFA into biogas (CH4, CO2) and leachate get dominated by
non-biodegradable compounds such as humic substances. This phase of mature
landfills is known as methanogenic phase (Chian and De Walle 1976). The health
problems related to various emissions from landfills include high PM10 exposure,
breathing problems, bacterial infections, increased mucus production, asthma, ele-
vated cardiovascular risk, and other infections. Vector-borne diseases such as dengue
and cholera are also rising. This is also affecting our environment adversely. The
greenhouse gases produced due to the decomposition of organic waste in landfill site
cause the climate change, whereas the contaminants that percolate in lower soil and
groundwater lead to soil and water pollution. So the three major problems related to
landfills that affect the environment and humans adversely include leachate, toxic
substances, and greenhouse and toxic gases.
Leachate: A Toxic Soup
The highly contaminated wastewater that is formed in the landfill when waste is
subjected to physicochemical and biological transformation is called leachate. The
percolation of rainwater through landfill and inherent water present in waste lead to
the formation of leachate. The quantity of leachate is affected by the climate, as the
input via precipitation and loss via evaporation depend on it. It has been observed
that leachate production is greater in less compacted waste as compaction reduces
the filtration rate (Lema et al. 1988). According to the landfill age, weather variation,
precipitation, waste type, and composition, the quality and quantity of leachate are
greatly affected in different landfills. So the flexible method or combinations
of leachate treatment methods are required to get rid of the leachate problem
326 Swati et al.
(Baig et al. 1999). Leachate is classified as recent, intermediate, and old as per the
stages of waste evolution which go through different stages: aerobic, acetogenic,
methanogenic, and stabilization stage (Welander et al. 1997; Wang et al. 2003;
Harsem 1983; Chian and De Walle 1976). The basic parameters that are used to
characterize landfill leachate include biological oxygen demand (BOD), chemical
oxygen demand (COD), suspended solids (SS), the BOD/COD ratio, ammonium
nitrogen (NH3-N), total Kjeldahl nitrogen (TKN), heavy metals, and pH (Chian and
De Walle 1976).
The leachate finds its way to the environment from the bottom of the landfill, from
where it enters into the groundwater through the unsaturated soil layers which later
on mixes with surface water via hydraulic connections. Sometimes the untreated and
partially treated leachate is directly discharged into water bodies which results in
pollution. It poses a high risk to water resources if not managed properly (Ikem et al.
2002). The pollution potential of leachate depends upon various factors such as the
leachate concentration, landfill location, i.e., hydrogeological setting, landfill type
(engineered or not), and the quality and volume of the receiving water (groundwater
or surface water) (Islam et al. 2013). Leachate problem is getting great attention of
researchers because of its adverse effects on human being and environment which
are represented by groundwater and surface water contamination and toxicity to
humans (Kjeldsen et al. 2002). So the leachate treatment before its ultimate disposal
is necessary. It has been observed that most of the landfills operating in India are
non-engineered, i.e., devoid of proper bottom liner and leachate collection system
which is worsening the situation. This leads to the percolation of leachate in the
lower layers of landfill soil and hence causes groundwater pollution of surrounding
area (Kanmani and Gandhimathi 2012). The areas near to dumping site have the
greater probability of groundwater contamination which poses a substantial risk to
local groundwater resource user and the natural environment. The surface and
groundwater contamination through landfill leachate has gained the interest of
researchers in recent years, and they assessed the effect of landfill on water resources
via different approaches (Saarela 2003). They determined the experimental value
of impurities in groundwater or estimated it through mathematical modeling
(Moo-Young et al. 2004).
Nagarajan et al. (2012b) have carried out research on the impact of landfill leachate
on groundwater in Erode city of Tamil Nadu, India. They found that groundwater has
high electrical conductivity and high concentration of dissolved solids in the areas
near to the landfill sites. Also, groundwater in the nearby areas was brackish in
nature. This renders it unfit for drinking and also causes gastrointestinal problem in
humans (Malakootian and Dowlatshahi 2007; WHO 1997). Although most of the
groundwater samples were found to belong to low-sodium class. Hence, it can be
used for irrigation purpose (Subramani et al. 2005). The other report of the Bhalswa
Lok Shakti Manch and hazards center of New Delhi in 2012 showed that the volatile
organic chemicals present in landfill leachate such as chloroform, benzene, ethyl-
benzene, toluene, etc. cause skin and eye irritation (Jhamnani and Singh 2009).
Other problems that are found to be associated with contaminated water include dry
skin, ringworm infection, skin allergy, pigmentation, rash and eye problems, etc.
Toxic Substances
The unsegregated waste that ends up in landfill contains lot of toxic substances
which include waste from industries, pharmaceutical companies, hospital, e-waste,
etc. These substances are highly recalcitrant and pose a great risk to human life and
environment. With increased industrialization, the usage of mechanical devices and
machinery is also increasing such as television, batteries, and computers which
contain the substances like lead, arsenic, cadmium, PVC, acids, and others. The
improper disposal of these materials into the landfill leads to the accumulation
of toxic substances in landfill. Other toxic substance that is frequently detected
in landfill is mercury which is found to be released from fluorescent light bulbs.
Even a small amount of mercury vapor poses a great risk to human kidneys
and lungs. Eventually, these substances leach into groundwater and soil and
cause pollution.
Greenhouse Gases
Landfills have a layered structure of waste and soil. Each layer of waste that is added
into the landfill is compacted which removes oxygen and excess moisture from
it. This leads to the breakdown of products anaerobically which over the time
produces methane gas. The release of methane and other gases (mainly carbon
dioxide) from landfill is also one of the major problems linked to landfills. Globally
the 13% (818 million metric tons per annum in terms of CO2 equivalent) of the
methane emission occur from landfills (Rachel et al. 2007). Methane is 25 times
more potent greenhouse gas than carbon dioxide that leads to global warming and
climate change. The disposal of municipal solid waste in landfills becomes a
significant source of methane emission globally. It is highly flammable gas which
causes fires and explosions in landfills if present in high concentrations (Sridevi et al.
2012). Some of the treatment methods have been used to reduce the production of
methane gas such as open window or tunnel composting and in-vessel composting.
Anaerobic digestion is also used but in the confined place so that released methane
gas is captured easily and converted into energy. Composting is also one of the
possible solutions to reduce organic waste and hence the production of methane.
With the increasing urbanization and population growth, the amount of waste
generated is also increasing which demands the need of other disposal methods and
alternative solutions to waste disposal problem. A study was conducted on the
emission of methane from Delhi’s landfill site which reveals that 91.23 Gg/yr.,
3845.20 Gg/yr., and 77.42 Gg/yr. of methane were emitted from Bhalswa, Ghazipur,
and Okhla landfill sites of Delhi. The methane emission is increasing day by day
with increasing population and consumption of resources; hence the mitigation steps
are the need of the hour to control GHG emission from landfills. The segregation of
organic waste at the source point itself will prove very helpful in reducing the
organic fraction of waste in landfill which in turn reduces the formation of green-
house gases in landfills. Landfill gases (methane and carbon dioxide) have a great
328 Swati et al.
fuel value; hence it can be tapped from landfills and utilized as an energy source. So
the construction of sanitary landfills having a gas tapping system will prove highly
beneficial in the future (Kumar and Sharma 2014; Gupta and Singh 2015).
About 16 million metric (CO2 equivalents per annum) of methane is emitted in
India from landfill sites (International Energy Agency 2008). Many researchers have
studied the energy potential from landfill gas of different landfills sites of India such
as Mumbai (Deonar and Gorai) with 5.6 MW, Ahmedabad (Pirana) 1.3 MW, Delhi
(Bhalswa, Ghazipur, and Okhla) 8.4 MW, and Pune (Uruli) 0.7 MW annually
(Siddiqui and Khan 2011). The methane is finally converted into primary constitu-
ents such as carbon dioxide and water during the process of energy production which
reduces its effect on climate as methane is 25 times more potent greenhouse gas than
carbon dioxide. A report by the Planning Commission (2014) has revealed the
potential of waste as a resource and indicated that 62 million tons of waste which
is generated annually can produce 72 MW of electricity from landfill gas, 439 MW
from combustible component, and 5.4 million metric tons of compost from organic
waste. The United Nations Environmental Program (UNEP) has conducted a study
that shows that emission of gases can be reduced by employing a number of
management practices such as recycling and reuse of waste, waste minimization,
reduction in fossil fuel use as energy is recovered from waste combustion, and using
CH4 from landfill to meet the in situ energy requirement (UNEP 2008, 2010).
Others
Breeding Ground of Pests

In India scenario, open dumps are highly prevailing which causes the breeding of
mosquitoes, flies, rats, cockroach, and other pests. Some diseases are very common
in the population living near the landfill site such as plague, histoplasmosis, murine
typhus, malaria, dengue, West Nile fever, etc. as they are caused by the pests
breeding in the landfills (Dawane and Gawande 2015).
Odor Problem
Odor problem is the other problem that is linked to landfills (Srivastava et al. 2014).
It becomes difficult for the people to live near the landfill site due to the foul smell of
waste decomposing in landfills. The problem is aggravated during summer season in
India, when the average temperature exceeds the 45 C mark (Dasgupta et al. 2013).
Air Pollution
It has been observed that the waste received by landfills is burnt in open fields to
reduce the amount of collected waste. This activity releases around 22,000 tonnes of
pollutants every year in the atmosphere of Mumbai (Annepu 2012). The fine
particles are also produced during open burning of waste which causes smog and
various respiratory diseases in humans (Sridevi et al. 2012). The improper manage-
ment of waste hence causes nose and throat infections, inflammation, bacterial
infections, breathing difficulties, reduced immunity, anemia, allergies, asthma, and
other infections (CPCB 2000).
Case Studies
Many states are actively involved in managing waste and trying different methods
and technologies available for developing sustainable waste management program
as per the need of the area and the state. The Pune Municipal Corporation (PMC) has
collected and segregated about 56% of waste with the help of SWaCH (an NGO) and
ragpickers. About 80% of the segregated waste has been treated and well processed
(PEARL 2015). A number of composting unit and waste-to-energy plants were also
established by PMC in different localities by involving private vendors into the
business. The private partnership involvement has not only saved 150 lakhs annually
to the PMC but also reduced the cost associated with environment degradation.
The Ahmedabad Municipal Corporation (AMC) has achieved a milestone by
collecting 98% waste. It has been possible because of the robust system developed
by the AMC. By keeping an eye on the projections of waste generation, AMC has
developed a detailed master plan for waste management in the state. It has developed
the first mobile court which deals with the violation of sanitation and health laws
(SWMD, AMC 2014). The AMC is spending `2,500 per metric ton of solid waste
which is not possible for the other municipalities and smaller cities. This became a
constraint for other states and cities. Some other NGOs and civil society organiza-
tions are actively involved in waste collection and management program in con-
junction with the municipalities of the state. Stree Mukti Sanghatana, a Mumbai-
based NGO, organized 3,000 waste pickers that cover around 10,000 household of
the city. Similarly, waste pickers in Pammal town of Kancheepuram district, Tamil
Nadu, collect 994 MT of waste monthly which belong to Exnora Green Pammal
(EGP) NGO.
Challenges
Although the PPP model is working successfully in different states, but still there are
few issues and challenges that need to be addressed. People have a notion that SWM
services are the responsibility of the government as the residents pay taxes for
various services so it becomes difficult to inculcate the habit of paying service
charges to private ragpickers employed by NGOs. An idea of collecting fee propor-
tional to the weight of the waste generated would inculcate the habit of recycling and
reusing of materials in humans. The landfills are receiving waste without segregation
that reduces its worth to generate energy and also increases the cost of processing
waste. So if the waste is segregated at the generator end only, then it will be highly
beneficial. But due to poor education and consciousness, it is also an enormous
challenge. Drafting solid waste management rules, which puts obligation on gener-
ator for waste segregation, will prove useful to eliminate the need of large landfill
areas. The availability of land for constructing new landfills within the city is
becoming difficult due to increased urbanization and increasing value of land. This
issue also needs to be addressed for successful waste management program. Waste
minimization in turn eliminates the need for more landfill area for waste disposal.
330 Swati et al.
So by encouraging households to itself manage biodegradable waste, the land

requirement for secondary segregation will be reduced. Government should also
direct its funds for the development of new technologies that help people in reducing
household waste. Also there is a need for characterizing waste of different regions
and make policies accordingly, as India has different climate zones, food habits, and
living standards.The composition of waste greatly affects its value as a resource for
energy production.
Recommendations to Solve Landfill Problems
Waste should be considered as resource which can be utilized to extract energy. This
notion can only solve the problem related to landfills. Landfill mining to extract
valuable substances for recycling, reuse, and recovery will lead to the proper
management of waste (ISWA 2012). India requires clear regulations and its enforce-
ment to solve problem related to waste management and landfills. Innovation in
technology related to manage landfills can only be brought about by strong regula-
tions and funds that can only be directed in this direction (Sridevi et al. 2012). The
investment in constructing engineered landfill sites and waste-to-energy facilities is
the only option that can help in solving the issues related to landfill. Methane
extraction and thermal treatment of waste are the major opportunities for energy
generation from landfills, but it requires qualified engineers and professionals having
experience in this field which are lacking in India. Resource recovery from waste can
be done using existing technologies as an extremely effective recycling tradition
exists in India. A well-coordinated network of “scrap dealer” produces around three
million tonnes of recycled materials which avoided the emission of 721 Kg CO2 per
annum in the environment in India (Annepu 2012).
Build New Sanitary Landfill
There are many issues and problems related to landfilling in India, but still it
continued to be an extensively accepted practice for waste disposal. Most of the
landfill sites in metropolitan cities like Delhi, Mumbai, Chennai, and Kolkata have
already exceeding their life span and are overflowing So the development of new
sanitary landfills or expansion of the existing landfill has been reported in many
states such as Delhi (Bhalswa, Okhla, and Ghazipur), Goa, Gujarat (8 sites), Andhra
Pradesh (Vizianagaram), Haryana (Sirsa and Ambala), Madhya Pradesh (Gwalior
and Indore), Maharashtra (Nashik, Sonpeth, Ambad, Pune, Navapur, and Navi
Mumbai), West Bengal (17 sites), Punjab (Adampur), and Rajasthan (Jodhpur)
(CPCB 2013). There are 59 constructed landfill sites, and 376 are under planning
stage in India as reported by CPCB (2013).
The properly engineered landfills are seldom found in emerging economies like
India. Most of the waste disposals occur in open dumps which are already exceeded
their life span and now converted into huge mountain of waste causing severe
environmental degradation and loss to natural resources. Sanitary landfill is the
answer to this problem which protects human health and key environmental
resources such as surface water, groundwater, soil fertility, and air quality (Kumar
et al. 2009; UNEP 2005). Other problems such as air emissions, odor, windblown
litter, fire hazards, and pest breeding can also be avoided by disposing waste in a
properly engineered landfill sites (MoEF 2000).
The foremost requirement to build a new landfill is the environmental impact
study of the proposed site which includes area of land required, composition of
underlying soil and bedrock, flow of surface water over the site, impact of proposed
landfill on local environment and wildlife, and historical or archeological value of
the proposed site. The sanitary landfills have various components that eliminate the
risk of leachate, GHG, etc. Sanitary (scientific) landfills have a base layer of clay
which is around 90 m thick, which arrests the seepage from landfill. The clay layer is
followed by drainage layer (made up of soil, 15 m thick) and vegetative layer
(minimize soil erosion, 45 cm thick). This is also called as leachate-collecting
layer as their main function is to collect leachate before it seeps underground. The
production of methane is reduced in sanitary landfills as most of the impurities are
soaked up by different layers. It can be said that sanitary landfills act as degassing
systems as methane generation speed is less as compared to ordinary landfills.
Sanitary landfills are also installed with vertical wells that regularly extract methane
from it which can be used for electricity and heat generation. Although sanitary
landfills reduce the risk to environment and human health tremendously, still India is
facing many challenges in building new sanitary landfills. Some of them can be
listed as lack of appropriate land, experienced engineers, and funds for landfill
construction.
Waste to Energy
The dumping ground can be freed from collected waste by directing it to the waste-to-
energy plants. Waste-to-energy technologies changed the perception of waste as a
resource. The waste composition is very important for energy recovery as present
technologies prove useful for waste having high-calorific value. Presently, the use of
waste-to-energy technologies can be proposed for India as more high-calorific value
waste is ending up in landfill now (Al-Khatib et al. 2010). Using this approach for
treating waste also depends upon the location, demographics, climate, and other
socioeconomic factors (Srivastava et al. 2014; Gomez et al. 2009).
Combustion of waste is the most widely used waste-to-energy technology that
provides heat and power (WER 2013). The integrated approach that utilizes recycling
and waste-to-energy conversion would significantly reduce the burden of waste in
landfills in India. New technologies that can convert unsegregated low-calorific value
waste into energy at economical value should be accepted as it will help in cleaning
the old landfill sites. Although some waste-to-energy plant exists in India, but they are
332 Swati et al.
not functioning properly due to various designs and operational problems. For exam-
ple, the first incinerator to treat MSW was built in Timarpur, New Delhi, in 1987. It
was a large-scale incinerator that has the capacity to process 300 tonnes of waste per
day and costs `250 million. But the plant failed because of seasonal variations in waste
composition and properties, poor waste segregation, inappropriate technology selec-
tion and maintenance, and operational issues (IUKR 2015). Despite this, waste-to-
energy technologies are going to play a key role in waste management in the future.
Recently, India’s largest waste-to-energy plant was launched at Narela-Bawana
landfill site that utilizes 2000 metric tonnes of waste every day to generate
24 megawatt of energy. This is the first scientifically engineered landfill site of
Delhi and is based on PPP (public-private partnership) model which involves the
collaboration of North Corporation with the Ramky Group, a Hyderabad-based
management company. The two other waste-to-energy plants are operating in
Ghazipur and Okhla landfill sites in Delhi which produce 12 megawatt of energy
from 2,000 tonnes and 1,200 tonnes of garbage, respectively. In spite of this, the
shortage of trained people in the waste management sector, inappropriate waste
policies, and waste technology selection are some challenges faced by India.
Conclusion
This paper reviewed the problem and issues related to waste disposal in landfills.
Landfill is the most economical way of disposing waste, but due to unengineered
nature, it poses a great risk to human health and environment. The present paper
emphasizes on building new sanitary landfills and treating waste by employing
various waste-to-energy technologies. This will solve most of the issues related to
landfill such as leachate, toxic substances, and greenhouse gases migration to the
environment.
Cross-References
▶ Investigation of the Chemical Content of Two Specific Streams in Municipal

Waste: The Case of Hazardous Household Waste and Dental Waste
▶ Management of Municipal Solid Waste in Morocco: The Size Effect in the
Distribution of Combustible Components and Evaluation of the Fuel Fractions
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Environmental Health Problems Due to Air
Pollution Exposure: A Case Study of 14
Respiratory and Associated Morbidities
Among Traffic Police Personnel in
Aurangabad City of Maharashtra
Suchirai Gaikwad, N. N. Bandela, Geetanjali Kaushik, and

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
Literature Review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
Aurangabad Scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
Data Collection Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
Distribution of Age Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
Use of Personal Protective Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
Other Self-Reported Morbidities Among Traffic Police Personnel . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
Peak Expiratory Flow Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
Sociodemographic Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
Work-Related Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
Routine Medical Checkups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
Peak Flow Restriction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
Other Associated Morbidities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
S. Gaikwad · N. N. Bandela
G. Kaushik (*)
Maharashtra, India
C. M. Hussain
Department of Chemistry and Environmental Science, New Jersey Institute of Technology,
Newark, NJ, USA

https://doi.org/10.1007/978-3-319-73645-7_169
338 S. Gaikwad et al.
Abstract
Air pollution is the major public health problem, and vehicular exhaust fumes are
the principal source of air pollution in urban areas. There is now a large body
of epidemiological evidences associating exposure to ambient particles with short-
and long-term effects on health. Traffic personnel undergo a sedentary style of
work as they are located at the traffic junctions where they are exposed to fumes,
vehicles, noise, and crowd. Majority of research papers on traffic police have
concluded that traffic police are at high stress that yield to body fatigue. Aurang-
abad is a rapidly growing city of Maharashtra with close to 11 lakh vehicles, 80%
of which are two wheelers. These vehicles are growing at a rate of 8% on an annual
basis. In order to manage this vehicle population, the Aurangabad has traffic
personnel posted across the city. However, no studies are available on the health
status of traffic policemen due to pollution. Therefore, this study is first of its kind
to understand this issue and to recommend relevant measures for improving their
health. This cross-section study was done in this context, among 100 traffic police
personnel in Aurangabad city, to assess the prevalence of respiratory and other
associated morbidities and the factors associated with it. The overall prevalence of
chronic respiratory morbidity was 28%. Out of the 100 police personnel, only two
reported the use of an appropriate respirator during their duty hours. Of those who
reported to use of face masks 97% of them used only some kind of face barriers like
kerchiefs or disposable masks that do not offer adequate protection. The major self-
reported morbidities among police personnel were low-back pain 38%, hyperten-
sion 21%, and diabetes 14%. The high prevalence of respiratory morbidity in traffic
policemen is a matter of concern since it may be due to their occupational exposure
to vehicular exhaust-related air pollution. Periodic monitoring of this group can
detect early signs of dysfunctions and measures including supply of appropriate
and acceptable personal protective equipments. Daily exercises, pranayam, and
yoga interventions are expected to improve the overall health and productivity of
the important work force such as traffic police.
Keywords
Respiratory · Morbidity · Traffic police · Personnel · Aurangabad
Introduction
Health is a state of complete physical, mental, and social well-being and not merely
an absence of disease. Health of a person is largely affected by the environment in
which they work, thus making occupation an important determinant of health.
Occupational hazards cause early deaths of millions of people worldwide and also
result in avoidable morbidity that adversely affects the quality of life. A recent World
Health Organization report placed occupational risks as the tenth leading cause of
morbidity and mortality. More than 80% of the global burden of occupational
disease as well as injury is borne by people in the developing countries since they
are home to about 70% of world’s working population. According to comparative
14 Environmental Health Problems Due to Air Pollution Exposure: A Case. . . 339
risk assessment carried out by WHO and ILO, enormous burden of mortality and
morbidity was attributed to occupational risk factors globally which accounted
for about 37% of back pain, 16% of hearing loss, 13% of obstructive lung disease,
11% of asthma, 10% of injuries, 9% of lung cancer, and 2% of leukemia, among the
exposed worker population (WHO 2006). Workers in developing countries are
disproportionately more affected than the developed economies due to several
factors including the presence of largely informal sector work force, weak or absent
regulatory frameworks, migration, cheaper and more hazardous production pro-
cesses, and low awareness. Occupational lung diseases rate as one of the most
common work-related illnesses and are therefore an issue of great priority in the
industrialized countries and also increasing rapidly in the developing countries.
There is now a large body of epidemiological evidences associating exposure to
ambient particles with short- and long-term effects on health (Adgate et al. 2002).
The health hazards get more severe when the exposure time increases. This is
observed prominently in situations as the personnel engaged in traffic duty. Traffic
personnel undergo a sedentary style of work as they are located at the traffic
junctions where they are exposed to fumes, vehicles, noise, and crowd. Their work
includes standing for longer durations, restricted to junctions loaded with idling
vehicles at the signals. Majority of research papers on traffic police have concluded
that traffic police are at high stress that yield to body fatigue (Rajan et al. 2014).
Aurangabad is a rapidly growing city of Maharashtra with close to 11 lakh vehicles,
80% of which are two wheelers. These vehicles are growing at a rate of 8% on an
annual basis. In order to manage this vehicle population, the Aurangabad has traffic
personnel posted across the city. However, no studies are available on the health
status of traffic policemen due to pollution. Therefore, this study is first of its kind
to understand this issue and to recommend relevant measures for improving
their health.
Literature Review
Occupational lung diseases is a major contributor to the global occupational disease

burden and is a main focus of occupational health programs worldwide. Estimates
indicate that work-related occupational exposure to airborne particulates accounts
for about 386,000 deaths and nearly 6.6 million DALYs worldwide. The bulk of this
is contributed by chronic obstructive pulmonary disease (COPD) followed by
asthma and pneumoconiosis. Occupational lung diseases broadly include those
that are specific to certain occupations like the farmer’s lung, asbestosis, etc. and
those that are aggravated by the work-related exposures like occupational asthma.
The nature of some jobs and the related exposures predispose certain groups
of workers to considerably larger risk of developing occupational lung diseases
(WHO 2010). Those in the textile, asbestos, steel, and coal mining industries,
construction workers, farmers, firefighters, spray painters, and mill workers who
are exposed to a range of dusts, mineral particles, and noxious chemicals are the
some of the most affected group. The most common occupational lung diseases seen
among the exposed workers have been bronchial asthma, byssinosis, silicosis,
pneumoconiosis, mesothelioma, chronic bronchitis, etc. Various studies have
shown the prevalence of byssinosis among textile workers ranges from 10.5% to
43.2%, chronic respiratory morbidity among mill workers ranges from 7.5% to
42.66%, and the prevalence of lung parenchyma changes among the construction
workers to be 15.4% (Hayes et al. 1994; Driscoll et al. 2005; Jeebhay and Quirce
2007; Nafees et al. 2013).
Besides the workers within the classic industrial settings, certain categories of
workers are highly vulnerable to develop occupational lung diseases due to chronic
exposure to high levels of ambient air pollution. Some of the workers studied include
bus drivers, taxi drivers, postal workers, shopkeepers, street vendors, garbage
collectors, toll booth workers, street sweepers, traffic wardens, and police personnel.
Though not working in settings with exposures to specific toxins or substances, these
workers and the nature of work they do are exposed to considerable amounts of
traffic-related ambient air pollution. They were found to have mainly chronic
respiratory diseases like chronic cough, chronic phlegm, and wheezing along with
decreased lung function in various studies (Burgaz et al. 2002; Wiwanitkit et al.
2008; Gupta et al. 2011; Patil et al. 2015). Rapid industrialization and urbanization
have aggravated the rising levels of ambient air pollution in the cities especially in
the developing countries including the Asian countries. The major share of the
traffic-related air pollution is due to the emissions from automobiles which in
many cities of the developing world do not follow emission standards.
Air pollution is the major public health problem, and vehicular exhaust fumes are
the principal source of air pollution in urban areas. A European assessment that
suggested air pollution accounts for 6% of all mortality and 50% of mortality due to
air pollution is accounted for by vehicular pollution (Künzli et al. 2000). The
hazardous traffic fumes contain a variety of pollutants such as particulate matter
(PM), carbon monoxide (CO), carbon dioxide (CO2), nitrogen dioxide (NO2), sulfur
dioxide (SO2), ozone, etc., all of which can cause respiratory problems and other
systemic diseases such as bronchitis, pneumonia, decreased lung function, and even
other health problems which include hearing impairment and eye-related problems
including cancer (Anderson et al. 2004). The respiratory effect due to exposure to
vehicular fumes could be both allergic and non-allergic in nature. In addition,
vehicular fumes also contain dangerous polyaromatic hydrocarbons like benzene,
toluene, and xylene which are classified as potentially carcinogenic and genotoxic.
PAH are of particular concern because their concentrations in the urban air are 10–30
times higher than rural air concentration (Suglia et al. 2008).
Since occupation is a major determinant of health, traffic police personnel face
multiple occupational hazards. They are continuously exposed to vehicular emis-
sions and work in noisy and polluted environment. Standing for long hours in a static
position makes them vulnerable to ergonomic problems further managing high
volumes of traffic density results in physical and mental fatigue among traffic
policemen. Both physical and mental health manifestations get accentuated with
the increasing length of service (Satapathy et al. 2009). Outdoor occupations in
general are hazardous in nature due to prolonged periods of exposure to high
concentrations of vehicular pollution putting the employees at increased risk of

respiratory and cardiovascular diseases (Mills et al. 2011).
Traffic police personnel are at the highest risk for the adverse health effect of air
pollution, compared to the general population. Occupational studies on traffic police
personnel help us to understand the effects of vehicular pollution and its specific
adverse effect due to the opportunity for defined exposures measurements (Brandt
and Watson 2003).
The majority of studies on traffic personnel investigated the effect of vehicular
pollution on the respiratory morbidity and the spirometric values correlated with it,
vitalograph (Saenghirunvattana 1995) or peak flow meter (Rahman et al. 2010;
Satapathy et al. 2009). Most of the studies showed a decreased lung function with a
significant reduction in the forced expiratory volume in 1 s (FEV1), forced vital
capacity (FVC), vital capacity (VC), and peak expiratory flow rate (PEFR), compared
to the control subjects. Cases of lung disorders were also observed (Suglia et al. 2008;
Karita et al. 2001; Laumbach and Kipen 2012; Singh et al. 2009; Pal et al. 2010; Ingle
et al. 2005; Gupta et al. 2011). The height of the police personnel and years of duty
were strong predictors of the pulmonary function in addition to age.
In fact, deterioration of the lung function showed a strong association with the
length of service in traffic police (Satapathy et al. 2009). Traffic police exhibited
higher respiratory signs and symptoms such as cough, phlegm, and rhinitis. A lower
lung function was associated with nonuse of protective masks among traffic police-
men (Holguin 2008). Some studies have looked at the effect of air pollution
on vascular inflammatory reactions in traffic policemen (Zimmerman 2012).
The prevalence of nonspecific respiratory disease (NSRD) showed an association
with a higher concentration of particulate matter in the air (Tamura et al. 2003).
In 2003–2004, a comparative cross-sectional study done in Jalgaon city, in
Maharashtra, India, among 60 nonsmoking traffic police and 60 healthy young adults
showed 40% of traffic police had frequent cough, 10% had shortness of breath, and
27% suffered from irritation in respiratory tract. The study also concluded that traffic
police have more respiratory impairment than the control group based on the spiro-
metric analysis done (Ingle et al. 2005). Various other studies done among traffic
police in India also showed decreased lung function, and it is evident with increase
duration of work period. Most of the abovementioned studies have presented their
results on the basis of relatively small sample size ranging from 30 to 60. Thus, there is
a need to conduct the study with larger sample size. Policing forms one of the major
work forces in the country. According to national data on police, the total police
strength in the country is about 26.34 lakhs as of January 2017. The data also shows
the sanctioned population per policemen is 576 where as in actual it is about 761.
Aurangabad Scenario
Aurangabad (“Aurang City”) is named after the Mughal emperor Aurangzeb. The
city is a tourism hub, surrounded by many historical monuments including the
Ajanta Caves and Ellora Caves, which are UNESCO World Heritage Sites. It is
the administrative headquarters of Marathwada region. By population it is the fifth

largest city in Maharashtra after Mumbai, Pune, Nagpur, and Nashik. Aurangabad
has a strategic position on the Deccan Plateau (Fig. 1). The city is surrounded by hills
of the Vindhya ranges, and river Kham a tributary of the Godavari River passes
through it. Major part of the city has deep black soil derived from the trap rock. The
weather, in general, can be said to be hot and dry. Temperature of Aurangabad city
varies between 9 C and 41.8 C. The total area under forest cover is about 557 km2,
which comprises of only 8.6% area of the total land area in Aurangabad (AMC
2016).
The city also has a very well-developed and organized industrial area which
surrounds the city on all sides. Waluj, Waluj 2, Chikalthana, Bidkin, and a new Five
Star Industrial Area Shendra are located in Aurangabad. The presence of large and
medium industries and an increasing number of vehicles in Aurangabad city make it
among the 17 non-attainment cities (Table 1) within the state (Jogdand et al. 2018).
Based on air quality assessment conducted by the MPCB, for the past 5 years,
annual PM10 concentrations have been above the National Ambient Air Quality
Standards.
The mass transport system for Aurangabad includes bus system and intermediate
public transport (sharing autos, autorickshaws). Two wheelers clearly (Table 2)
comprise a major proportion of Aurangabad city vehicle population. During the
period between 2015 and 2016, vehicles have shown a growth rate of 8% from
1,020,021 to 1,102,444.
MSRTC (Maharashtra State Road Transport Corporation) started the bus service
with 29 buses on 11 routes but that has fared poorly due to a variety of reasons. In the
absence of proper public transport facilities in the city, thousands of school and
Fig. 1 Location of Aurangabad city. (Source: Environment Status Report Aurangabad

(2013–2014))
Table 1 Pollutant concentrations in Aurangabad city (μg/m3)

Sr. No. Location PM10 SO2 NO2
1. CADA Office, Garkheda 80 15 41
2. SBES College Campus 115 16 43
3. Collector’s Office 82 11 34
Source: http://cpcbenvis.nic.in/airpollution/2016/National%20Ambient%20Air%20Quality%
20Monitoring%20Programme%20(NAMP)%20Data%202,016,%2007.11.2017.pdf
Table 2 Vehicle S. No. Category Number

population
1. Motorcycles 735,794
2. Scooters 84,168
3. Mopeds 46,939
4. Total 2 wheelers 866,901
5. Motor cars 55,123
6. Jeeps 29,314
7. Station wagons 452
8. Taxi meter fitted 21
9. Taxi tourist cabs 2596
10. Autorickshaws 26,529
11. Stage carriages 5614
12. Contract carriages 1375
13. School buses 1008
14. Pvt. service. veh. 1989
15. Ambulances 490
16. Trucks and lorries 13,119
17. Tankers 4712
18. Del. van (4 wh.) 24,888
19. Del. van (3 wh.) 29,960
20. Tractors 23,285
21. Trailers 14,689
22. Others 379
Total number of vehicles 1,102,444
Source: Transport Maharashtra, 2016
college students, traders, office-goers, and commoners have to rely on the 26,000
odd autorickshaws or private vehicles plying in the city.
This has drastically increased the number of vehicles on city roads and ultimately
put a burden on the infrastructure. The city buses face great inconvenience in plying
in about 40% of the old city area due to traffic congestion.
The road infrastructure development has not kept pace with the sudden increase
in the number of vehicles which is leading to high traffic congestion in the city and
thereby exceeding the air quality standards. The presence of large and medium
industries and an increasing number of vehicles within the city make it among the
Table 3 Data collection Total number of chowks selected (5) 1. Nagar naka
locations 2. Mahavir chowk/ Baba
petrol pump
3. Kranti chowk
4. Doodh Dairy + Seven
hill
5. Cidco
Total number of traffic police 100
personnel from the
selected chowks who were
interviewed and assessed
17 non-attainment cities within the state of Maharashtra (Jogdand et al. 2018). In the
absence of studies undertaken among traffic cops which addresses the general health
status, this study was conceptualized to assess the respiratory and other associated
morbidities among the traffic police personnel in Aurangabad city.
Methodology
The study was a cross-sectional survey conducted in five traffic stations or chowks in
Aurangabad city with the high prevalence of traffic selected from within the city.
From each station all the police personnel who met the eligible criteria were included
in the study. The study population comprised of 100 police personnel (Table 3)
within the age group of 25–58 years working in the city at least for the past 1 year
and currently continuing at the same post since January 2017. Police personnel with
previous history of respiratory illnesses (asthma, TB, COPD) and chest injuries,
surgeries, cardiac failure before joining the job were excluded from the study.
Interview and monitoring/checking of peak flow readings, Blood pressure and
sPO2 off the personnel was done at their convenience. Each chowk was visited at
least two to three times to cover traffic police personnel.
Data Collection Technique
The data was collected through a structured interview schedule using validated
questionnaire.
(a) Interview schedule

A structured interview schedule using combined and modified version of the
OSHA Respiratory Questionnaire was used.
The above standard questionnaire is internationally accepted and validated.
Few changes were done in this above questionnaire as few basic information
questions were added. Questionnaire was translated into Marathi language and
was validated.
(b) Peak flow meter measurements
Peak flow rate was measured using a portable Mini Cipla peak flow meter. All
the study subjects were asked to take a maximal deep breath, place the peak flow
meter in their mouth, and expire out through the mouth as hard and as fast as
possible into the apparatus in the standing position after demonstrating the
procedure to them. The best of three efforts was taken as the peak flow value
for analysis and was entered into the peak flow metric analysis sheet, which
contains a scale for specific age, sex, and height. The respondents value was
compared with the reference value and thereby and was interpreted as having a
normal or obstructive pattern.
(c) Blood pressure measurement
(d) sPO2/blood oxygen saturation levels
Results
The study was done among 100 traffic police personnel who have worked in the
Aurangabad city at least for the past 1 year. The mean age of the study population
(Fig. 2) was 42 6 years (range, 25–58 years).
Distribution of Age Group
The presence of familial history of chronic respiratory disease for either father or
mother was reported by 19% of the respondents and 7% of them reported history of
severe respiratory morbidity within 3 years which made them to stay away from job.
70
60
50
40
30
20
10
0
25-32 32-46 46-58
Series 3 Series 2 Series 1
Fig. 2 Mean age of traffic policemen

Table 4 Use of personal Variable (N = 100) Frequency (%)

protective equipments
Use of face mask during traffic duty:
among police personnel
No 82
Yes 18
Type of face mask:
Respirator 02
Others (disposable mask, kerchief) 16
Reasons for not using face mask:
Unavailable 94
Uncomfortable 28
Undergo regular health checkup:
Yes 34
No 66
Use of Personal Protective Equipment
Major proportion of the respondents (82%) reported that they never use face mask
while traffic as well as patrolling duty. Only 2 personnel out of 100 reported the use
of respirator as face mask. Twenty-eight percent of the respondents reported that it is
uncomfortable to use the face mask, and it is difficult to blow the whistle with mask
on face (Table 4).
About 28% of the subjects who reported wearing face mask was uncomfortable
also specified the reason. Seventy-three percent of them reported it hinders their
wireless communication process, and 25% of them mentioned the problem of
differential tanning of the face that the mask causes.
Other Self-Reported Morbidities Among Traffic Police Personnel
From the study, 54% of the police personnel reported to have hypertension, 18%
reported of having diabetics, and nearly 7% had the problem of varicose veins. The
most prevalent musculoskeletal problem reported among police personnel was
low-back pain which was about 48%. Also, the sPO2 monitoring with the pulse
oximeter has reported 17% cases (Table 5).
Prevalence of respiratory morbidity among police personnel in Aurangabad
city in the past 1 year can be shown in the form of a pie chart (Fig. 3).
1. Cough: From the study, 7% reported to have frequent cough and 6% reported to
have chronic cough.
2. Phlegm: 15% of them reported frequent phlegm, and 13% of them reported to
have chronic phlegm.
3. Wheezing: 10% reported the problem of frequent wheezing, and 4% had chronic
wheezing.
Table 5 Other self- Variable (N – 100) Frequency (%)

reported morbidities
Hypertension 54
among police personnel
Varicose vein 07
Diabetes 18
Ophthalmic 62
Musculoskeletal
Low-back pain 48
Shoulder pain 13
Knee pain 32
Neck pain 38
Fig. 3 Prevalence of
respiratory morbidity among 28
police personnel
48
PEFR
BP
sPO2
54
Opthalmic
Msk
62
17
4. Dyspnea: 18% of the respondents reported Grade 1 dyspnea, while 9% reported

to have Grade 2 dyspnea.
5. Peak flow restriction: 28% of the respondents presented with peak flow restric-
tion, which meant their peak flow readings are less than the normal range
according to one’s age, sex, and height.
Association of chronic respiratory morbidity with work-related factors:

Traffic police personnel who worked in the traffic department, with higher seniority,
worked in the city for more than 6 years, posted in the day shift frequently for the
past 1 year, worked near roadside for more than 6 h per day, and who did traffic duty
had higher chronic respiratory morbidity. Peak flow restriction showed a significant
association with increase in age. Police personnel aged more than or equal to
40 years had significantly higher odds of getting peak flow restriction when com-
pared to those aged less than 40 years. Similarly police personnel with familial
history of chronic respiratory morbidity (either father or mother) significantly had
higher odds of getting peak flow restriction when compared to those without any
familial history factors like tobacco use and use of any face barriers on traffic duty,
and place of residence showed no significant association with peak flow restriction.
Peak Expiratory Flow Reading
The mean peak flow meter reading among male police personnel was 430 70 l per
minute (L/mt). PEFR shows mean peak flow meter reading was significantly differ-
ent among different age group in males.
Discussion
Occupational morbidity studies in India have mostly been among industrial workers
exposed to occupational hazards. Workers who are continuously exposed to high
levels of ambient air pollution due to the nature of their job, however, have attracted
less attention.
This study was done in this context, among 100 traffic police personnel in
Aurangabad city, to assess the prevalence of respiratory and other associated mor-
bidities and the factors associated with it. The overall prevalence of chronic respi-
ratory morbidity was 28%. This overall prevalence of chronic respiratory morbidity
among the study population is higher compared to prevalence figures reported by
community based studies in India, which range from 2% to 8.5%. A large multi-
centric study carried out by the ICMR in 2006 reported a prevalence of 5% among
men and 3.2% among women (Jindal 2012).
Data regarding chronic respiratory morbidity available from population-based
studies from other developing countries include those from a study done among the
elderly in Bangkok with a prevalence of 7.1% and 4.65% among adults in Iran. A
high prevalence of chronic respiratory morbidity of about 17% was reported from
among Korean adults over 45 years of age (Maranetra et al. 2002; Golshan et al.
2001; Kim et al. 2005).
The prevalence of chronic cough, chronic phlegm, and chronic wheeze was sepa-
rately analyzed in the present study and was found to be 6%, 13%, and 4%, respectively.
Prevalence figures of chronic cough have been reported from community-based studies
from various parts of India. It ranges from 2.2 to 2.4% in rural areas and 1.7 to 2.5% in
urban areas (across different study sites in India). However the operational definitions
for chronic cough and phlegm used by the different studies vary from “cough at night,”
“cough in the morning” and “phlegm in the morning,” cough and phlegm “without a
cold” “on most days” and “for at least 3 months” from the current study that used the
definition as cough/ phlegm for 3 or more consecutive months.
The prevalence of chronic phlegm in the present study was 12.3%. In comparison
the figures from other studies in India have reported a chronic phlegm prevalence of
1.9%–4.4%, 2.6%, and 1.2%. The prevalence of cough was found to be between 2.4
and 5.6% in the rural areas and 1.7 and 5.4% in the urban areas in different centers in
India.
Comparison with other occupational groups exposed to outdoor air pollution. The
chronic respiratory morbidity prevalence which was 28% among the police person-
nel in this study was higher in comparison with other occupational groups that are
similarly exposed to air pollution that is mostly traffic related. A study done among
street sweepers in Nagpur, India, showed a prevalence of 6% (Sabde and Zodpey
2008). Another study done among traffic police in Bangkok found that the preva-
lence of cough and phlegm among them was 18.6% (Wongsurakiat et al. 1999).
The low prevalence among street sweepers could be due to the fact that the
duration of exposure to ambient air pollution among them may be lower than that of
the traffic police due to the differences in the work timings. Mostly street sweepers
carry out their work in the early morning or late evening that may be before or after
the rush hours of traffic.
Sociodemographic Factors
Tobacco smoking was reported by 14% of the male traffic personnel. Though studies
have linked tobacco and chronic respiratory morbidity, there was no relationship
noted between tobacco use and chronic respiratory morbidity in the current study.
The fact that the prevalence of tobacco use among the police personnel was much
lower than the overall figures for men in Aurangabad the possibility of under
reporting of tobacco use, it is also noted here that observationally during the study,
some of them who had reported nonuse were smoking in the adjoining rest room.
The possible links between tobacco use among men and biomass fuels among
women could be explored in connection with the respiratory morbidity among this
group in the future.
Work-Related Factors
Number of Years of Service in the City

The study has showed that the police personnel who worked in the city for more than
6 years had 2.98 times higher odds of having chronic respiratory morbidity when
compared to those who worked in the city for less than or equal to 6 years. The peak
flow restriction was high among those whose service years were more than 6 years in
the city. Similar study conducted among traffic police in Patiala city, India, also
showed that the peak expiratory flow rate (PEFR) was lower in those with more than
8 years of service in the city (Gupta et al. 2011). The increased years of service could
indicate higher total exposure for a longer duration of time and therefore adversely
affecting the lung function.
Type of Shift
The study showed that 22% of the police personnel posted frequently during the day
shifts in the last 1 year had higher chronic respiratory morbidity when compared to
14% of those who did 24-h duty for 3 days in a week. This may be due to the reason
that personnel posted to day shift are posted to specific locations where they have to
be present from morning 8 am to evening 7 pm (the rush hours of traffic), whereas
those on 24-h duty do not have to be in a specific location and move from one place
to another while on patrol in vehicles.
Use of Personal Protective Equipments During Traffic Duty

Out of the 100 police personnel, only 2 reported the use of an appropriate respirator
during their duty hours. Of those who reported to use of face masks, 97% of them
used only some kind of face barriers like kerchiefs or disposable masks that do not
offer adequate protection. This could explain the high chronic respiratory morbidity
among those who reported any kind of face barriers during traffic duty. Though the
police personnel seem to think that the barriers offered them protection from air
pollution, the fact is that other than the prescribed respirators, handkerchiefs and
disposable tissue masks does not reduce their exposure to ambient air pollutants.
A study from Bangkok highlights this by its finding that policemen, who used the
prescribed face masks, had significantly lower respiratory morbidity when compared
to those who did not use them (Wongsurakiat et al. 1999). The use of face barriers of
any kind was also found to be higher among those who had more than 6 years of
service in the city. Those with 6 years or more of service in the city had higher
prevalence of respiratory morbidity and therefore could have used face barriers as a
as a precaution during their duty time.
This is an area of potential intervention for the protection of the traffic police force
from avoidable occupational respiratory morbidity. Police personnel who were
diagnosed with any morbidity in the past 1 year were found to use face barriers of
any kind significantly more than those who did not have any morbidity. In addition
to the above findings, the policemen revealed two major reasons for nonuse of face
masks while on traffic duty. The subjects who reported wearing face mask was
uncomfortable and also specified the reason. Some of them reported it hinders their
wireless communication process and few of them mentioned the problem of differ-
ential tanning of the face that the mask causes.
Routine Medical Checkups
The study revealed that more than half of the respondents do not attend periodic medical
health checkups. They reported unofficially during the interview that though the
periodic checkups are officially mandatory, they are not taken seriously and are merely
customary as far as the personnel and the medical officers are concerned. This exposes a
huge gap that can be addressed by the higher authorities by making the mandatory
checkups more structured, serious, and an opportunity for monitoring the health of its
personnel. Police personnel have to work for a minimum of 6–8 h per day, and they do
have duties on all 7 days in a week which also disregards their need for training
regarding occupational health issues and PPEs and also regular monitoring through
health checkups. Various studies have pointed the need for creating awareness among
the police personnel to undergo regular and effectively carried out health checkups.
Peak Flow Restriction
The overall prevalence of peak flow restriction among police personnel in this study
was 28%. This prevalence of peak flow restriction in this study is similar to the study
conducted in Bangkok where 21% of the traffic police personnel had abnormal air
flow on spirometry (Wongsurakiat et al. 1999). The peak flow restriction among the
police personnel was significantly associated with working in the traffic department,
age above 40 years, higher seniority, working near roadsides for more than 6 h per day,
and those who were posted in the day shift frequently in the past 1 year. All these could
be surrogate indicators of higher duration and higher magnitude of the exposure to air
pollution that is mostly traffic related; they are exposed to by the nature of their work.
Other Associated Morbidities
The prevalence of other associated morbidities was hypertension 21%, lower back
pain 38%, and diabetes 14%. This is comparable with other studies in India
conducted among traffic police where the prevalence of hypertension ranged from
27.9% to 45%. About one in two police personnel reported low backache and is
similar to that reported by a similar study conducted among police force in Kerala
(Johns 2012) which reported a low backache prevalence of 38%. This also stresses
the need to focus on the risk of specific occupational morbidity that the traffic police
personnel are vulnerable to due to the nature of their occupation.
Conclusion
The overall prevalence of chronic respiratory morbidity among police personnel was
28% within age group of 25–58 years in Aurangabad city. It was high compared to the
general population and comparable to industrial workers of India. About one in five had a
peak flow restriction indicating some respiratory impairment which needs further explo-
ration. The major self-reported morbidities among police personnel were low-back pain
38%, hypertension 21%, and diabetes 14%. The high prevalence of respiratory morbidity
in traffic policemen is a matter of concern since it may be due to their occupational
exposure to vehicular exhaust-related air pollution. Preemployment as well as periodic
medical surveillance could be made more structured including serial lung function
measurements using validated and standardized spirometry to detect those at risk and
initiate appropriate preventive measures. The study also reveals high blood pressure
levels and deficient sPO2 in few cases. Musculoskeletal conditions which include low
backache among the police personnel suggest the need for an occupational health
assessment and remedial measures. Periodic monitoring of this group can detect early
signs of dysfunctions, and measures including supply of appropriate and acceptable
personal protective equipments could be taken. Daily exercise, pranayam, and yoga
interventions will improve the overall health and productivity of a critical work force like
traffic police.
Cross-References
▶ Air Pollution
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Microplastics as Contaminant in
FreshWater Ecosystem: A Modern 15
Environmental Issue
Muafia Shafiq, Abdul Qadir, and Chaudhery Mustansar Hussain
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
Microplastics in Freshwater Ecosystems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
Techniques for Detection and Characterization of Microplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
Sampling Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
Sample Processing Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
Segregation of Organic Matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
Identification and Characterization of Microplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
Environmental and Health Effects of Microplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
Impact of Microplastics on Freshwater Biota . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
Microplastics Toxicity to Aquatic Organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
Effect on Energy Reserves and Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
Effect on Reproduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
Bioavailability of Additives and Adsorbed Environmental Contaminants . . . . . . . . . . . . . . . . . 369
Trophic Transfer of Microplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370
Legal Framework for Microplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
Future Considerations and Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
M. Shafiq
College of Earth and Environmental Science (CEES), Faculty of Science, University of the Punjab,
Lahore, Pakistan
Biotechnology and Food Research Centre, PCSIR Laboratories Complex, Lahore, Pakistan
e-mail: organicfoodlab@gmail.com
A. Qadir
College of Earth and Environmental Science (CEES), Faculty of Science, University of the Punjab,
Lahore, Pakistan
e-mail: qadir.qau@gmail.com
C. M. Hussain (*)
Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark,
NJ, USA
e-mail: chaudhery.m.hussain@njit.edu

https://doi.org/10.1007/978-3-319-73645-7_172
356 M. Shafiq et al.
Abstract
Plastic pollution emerged as an environmental problem during last quarter of
twentieth century. This emerging pollution in aquatic ecosystems is degrading
the food web and ecological integrity and posing hazardous effects on the
environment. Plastic debris, fragments, fibers, and beads are the microplastics
having size less than 5 mm and complex entities that persist within the
environment for longer times. Recently, several scientists have reported the
accumulation of microplastics in aquatic ecosystems all over the world.
Most of the reports highlighted the marine environment, whereas limited litera-
ture is available to address the microplastics in freshwater ecosystems.
This chapter highlights the sources, abundance, polymer type of microplastics,
and recent developments in the methodology and discusses the questions
focusing on its toxicological effects on freshwater biota. Current scientific
literature reviews the different methods for microplastics sampling strategies
on spatial and temporal scales, separation, identification of microplastics, and
their impacts on ecological integrity of freshwater ecosystems. Furthermore,
several studies have been conducted on the transfer of microplastics from terres-
trial ecosystem to freshwater bodies and how it becomes the part of human food
chain. This chapter will be helpful in increasing the understanding for the
development and implementation of appropriate policies related to plastic
pollution.
Keywords
Microplastics · primary microbeads · freshwater ecosystem · Pyrene ·
Fluroanthene · toxicity to biota · Munich plastic sediment separator · PMEH
programme · Secondary microplastics
Introduction
Plastics are synthetic organic polymers, which are resulting from polymerization
of simple petroleum-based monomers (Cole et al. 2011; Kumar et al. 2018).
These synthetic polymers are durable, inert, lightweight, having excellent
electrical and thermal insulation properties and could easily be molded in any
desired shape (Andrady 2011). These attribute make it a most desirable material
used in almost all sectors of modern human society, with vast variety of
purposes. The benefits of plastics are extensive, but it has some serious ecological
risks. Plastic is synthetic xenobiotic nondegradable products, which has no natural
process for its degradation. Its stability and non-biodegradable properties make
it an attractive material in modern usage (Barnes et al. 2009; Sivan 2011).
The manufacturing of plastic products has been tremendously increased from
1.5 million tons to 288 million tons during the last 70 years (Dris et al. 2015).
Due to high production and non-biodegradable properties, plastic waste has
been increased all over the world. According to (Dris et al. 2015), only 26.3% of
15 Microplastics as Contaminant in FreshWater Ecosystem: A Modern. . . 357
all plastic waste is reused in Europe. Due to poor waste management, plastic is
continuously entering the freshwater environment ultimately leading to marine
environment (Sivan 2011). The long-term persistence and amassing of large
quantity of this anthropogenic litter build up the plastic islands in pelagic gyres
of the Atlantic and Pacific oceans (Hidalgo-Ruz et al. 2012). The accumulation of
large volume of plastics indicates the careless behavior of man to nature and
environment. Macroplastics are broken into small pieces and easily ingested by
the aquatic organisms. Even macroplastics and microplastics both release
different organic chemicals, which diffuse in the body of aquatic organism and
disrupt the physiological integrity of organism as well as ecosystem (Sutherland
et al. 2011).
Microplastics in Freshwater Ecosystems
The release of toxic compounds and microscopic particles from plastic decomposi-
tion in water bodies has attracted the scientific community, and nowadays it
has become a sensitive environmental problem (Cole et al. 2011; Imhof et al.
2012). In recent years, the debates have been shifted from macroplastics to an
unseen form of plastic pollutants. Although these small invisible particles have
been detected in 1970, these particles received more attention in 2004 and named
as microplastics. Microplastics exist in the form of small microscopic particles
having size <5 mm and further categorized by numerous authors in to large
(1–5 mm) and small microscopic particles (<1 mm) (Imhof et al. 2012; Eriksen
et al. 2014).
Sources of Microplastics
Microplastics are not a homogeneous group of materials and exhibiting diverse
physiochemical properties related to their emission sources. Diversity in size,
shape, composition, and polymeric additives of microplastics may attribute
the properties that influence their biological effects. On the basis of sources, micro-
plastics can be categorized in to two groups:
1. Primary microplastics
2. Secondary microplastics
Primary microplastics are specially engineered for diverse functions such as

scrubbers in cleaning and personal care products or may be in the form of pellets
used as feed stock for plastic production (Gregory 1996; Fendall and Sewell 2009;
Cole et al. 2011). Secondary microplastics are resulted from degradation of
macroplastic litter including synthetic clothing fibers, fishing net, industrial raw
materials, polymer fibers, household items, plastic films, foamed plastics, consumer
products, etc. caused by mechanical abrasion, ultraviolet radiation, and microbio-
logical degradation (Hidalgo-Ruz et al. 2012; Free et al. 2014).
Distribution and Occurrence of Microplastics

The rate of distribution of microplastics in the environment varies
depending upon physical and biological factors. Microplastics that were identi-
fied connected to various origins both primary and secondary sources,
having different compositions and indicated spatial association between types
of observed microplastics and anthropogenic activities. Near plastic
processing plants, manufactured pellets has been found abundantly, whereas
microbeads and scrubbers may found in industrial and household waste-
water, where they enter into the drainage system and move into rivers and
estuaries (Hidalgo-Ruz et al. 2012). Microplastics have been reported from
freshwater bodies (Table 1) in different parts of the world such as rivers
of the USA, Europe, Asia, and Africa (Moore et al. 2011; Faure et al. 2013;
Hoellein et al. 2014; Castañeda et al. 2014; Lechner et al. 2014; Wagner et al.
2014; Sadri and Thompson 2014; Free et al. 2014). Plastic pellets were
observed in Danube, a freshwater body that has at large-scale plastic fabrication
plants nearby to it (Lechner et al. 2014), and plastic (micro) beads were
most plentiful in lake Erie and lake Huron industrial area (Zbyszewski and
Corcoran 2011). Abundant presence of secondary fragments instead of
primary pellets in the shores of less-occupied mountain lakes indicated a
source from the degradation of household things (Imhof et al. 2013; Free et al.
2014). A large number of studies in this emerging field indicate the complication
of the dilemma calling for scientific methods so as to identify and measure the
consequences of macro- and microplastic pollution for human health and
environment.
Techniques for Detection and Characterization of Microplastics
A huge body of knowledge related to microplastic detection techniques across

oceanic geographic habitats and locations have been reported. These techniques
are in general laborious, time consuming, describing the cost and microplastic
sampling difficulties from benthic and pelagic habitats, and unable to identify all
particles (Hidalgo-Ruz et al. 2012; Galgani et al. 2013). The process of microplastic
detection faces some challenges that include the methodology to recover plastic
particles from sediment and water samples, sort out plastic entities present in
sample from other inorganic particles, categorize the nature of observed
plastics, and then identify difficulties that arise due to formation of biofilms on
microplastics (Hidalgo-Ruz et al. 2012; Eriksson et al. 2013). Unfortunately same
methodologies are used for microplastic detection in freshwater ecosystems as
used in marine investigations. These techniques varied according to approaches
used for sampling, identification of selected sample, and finally enumeration/quan-
tification (Hidalgo-Ruz et al. 2012).
Table 1 Studies on microplastics in freshwater ecosystems (last 8 years)

Sample nature,
particle and mesh Polymera Maximum
Water Author size (where types abundance and
body name Continent studied reported) identified mean abundance
Vembanad Asia Sruthy and Sediment LDPE, 96–496 particles
lake Ramasamy samples, <5 mm PS, m2 with a mean
Kerala, (2017) particle, and 5 mm HDPE, abundance of
India mesh size PP 252.80 25.76
particles m2
Three Asia (Zhao et al. Surface water PE, PP, 100.0 items/m3
estuaries, 2014) PVC, etc. to 4100.0 items/
China m3
Lake Asia (Free et al. Surface water, Not Max: 44,435
Hovsgol, 2014) 0.335–0.999 mm, identified items/km2
Mangolia 1.00–4.749 mm, Mean: 20264
>4.75 mm and items/km2
333 μm mesh
St. North (Castañeda Sediment with PE Max: not
Lawrence America et al. 2014) 500 mm mesh, indicated
River, size classes: not Mean: 13759
Canada/ indicated (13,685) items/
USA m2
Highest mean
site density:
136926
(83,947) items/
m2
Danube Europe (Lechner Surface water, Not Max: 141647.7
river et al. 2014) <2 mm, 2–20 mm identified items/km3
Austria and 500 μm mesh Mean: 316.8
(4664.6) items/
km3
Tamar Europe (Sadri and Surface water, PE, PS, Max: 204 pieces
estuary, Thompson <1 mm, 1–3 mm, PP of suspected
UK 2014) 3–5 mm, >5 mm plastic
and 300 μm mesh Mean: 0.028
items/m3
Elbe, Europe (Wagner Sediment,<5 mm Not 64 items per kg
Mosel, et al. 2014) identified dry weight
Neckar, Mean: not
and Rhine indicated
rivers,
Germany
North North (Hoellein Not indicated Not Max and mean:
Shore America et al. 2014) 0.3–5 mm identified not indicated
Channel of
Chicago,
USA
(continued)
Table 1 (continued)
Sample nature,
particle and mesh Polymera Maximum
Water Author size (where types abundance and
body name Continent studied reported) identified mean abundance
Lake Europe (Imhof et al. Sediments and PP, Max:
Garda 2013) surface water, LDPE, 1108 983
(Italy) 9–500 μm, PS, PE items/m2
500 μm–1 mm, and PVC Mean: not
1–5 mm, >5 mm indicated
Lake North (Eriksson Surface water Not Max: 463423
Superior, America et al. 2013) 0.335–0.999, identified items/km2
Erie and >4.75 mm, Mean: 43157
Huron 1.00–4.749 mm, items/km2
Canada, 333
USA
Lake Switzerland (Faure et al. Sediment and Not Max: 9 items per
Geneva 2013) surface water, identified sample
<2 mm and (sediment),
< 5 mm 48,146 items/
(sediment), km2 (surface
<5 mm, >5 mm water)
(surface water), Mean: not
300 μm mesh indicated
Los North Moore et al. Surface, mid and PS Max: 12932
Angeles America 2011 near-bottom, items/m2
River, San >1.0–<4.75 mm Mean 24-h
Gabriel and 333, 500, particle counts,
River, 800 μm mesh size Coyote creek:
Coyote 4999.71 items/
Creek, m3, San Gabriel
USA river: 51, 603.00
items/m3, Los
Angeles River:
1146418.36
items/m3
Lake North (Zbyszewski Sediment PE, PP, Max: 3209
Huron, America and Corcoran and PET items/m2
Canada, 2011)
USA
a
High-density polyethylene (HDPE), low-density polyethylene (LDPE), polybutylene (PBT),
polyethylene tetraphthalate (PET), nylons, polypropylene (PP), polyvinyl chloride (PVC),
polystyrene (PS)
Sampling Types
Sediment Sampling
In the assessment of environmental conditions of any system, accurate and
representative sampling is the most important step of that study. There is two
ways of sampling including selective and volume-reduced or bulk sampling.
Selective sampling has been involved to surface sediments; however, volume-

reduced or bulk sampling has been adopted in sediments sampling or water parcels.
Sampling procedures differ on the basis of methodologies, volume sampled, and
also on the basis of sample locations. In order to avoid heterogeneities, Dris et al.
(2015) proposed a combined sampling approach for lakeshore sediment using
sediment core samples (depth 5 cm, 10 cm diameter), taking along a 20-m coastline
transect at a space of 2.5 m from one to another, which would give 4–6 L of
sample volume. For freshwater course like river, a diverse method should be useful.
As an alternative of running parallel to the waterline, the river bank might be
separated in to three small transects of 5 m expanded over the accumulation
zone perpendicular to the waterline (Dris et al. 2015).
Water Sampling
Till now, a comparison between outcomes of various freshwater systems
studies is very complicated because in those studies, nets with diverse mesh sizes
and locations for sampling were differed in depth and distance from the riverbanks.
The major challenge for method standardization is mesh size used for sampling,
having the property to retain smallest size plastic particles. A mesh size of
300–333 μm is used generally. The use of net with same mesh size in freshwater
system would allow comparing the data obtained from both sea and freshwater
environment. Sampling through the utilization of manta trawl may illustrate
an under estimation of microplastics having size smaller than mesh size.
This consideration is dire important because smaller particles possess more health
hazards to translocate organism’s tissues after ingestion (Dris et al. 2015; Wright
et al. 2013). Microplastic sampling from inshore water may face some technical
problems due to high suspended organic matter and clay minerals especially at
the time of leaf fall in autumn or during algal blooms which increase the possibility
of blockage of nets. This technical problem may limit the sampling time period
and consequently significant reduction of sampled volumes, suggesting the neces-
sary modification of manta trawl net in order to obtain sample from streams
and lakes. At the time of surface sampling from rivers in comparison to lakes,
continuous water flow and the velocity should be considered. Too slow (<0.1 m/s)
or too high current velocity may hamper high ram pressure on inflow of net.
Therefore, sampling of river water should be preferably carried out from a fixed
position. A second problem that arises at the time of sampling is a need for reference
unit to present particles per surface or per volume. In addition to find out load
fluctuation of microplastics in rivers, it is necessary to identify both dynamics,
temporal and spatial variability, of plastic particles (distribution in shore waters
and sediments) (Dris et al. 2015).
Sample Processing Methods
After sample collection, plastics are separated from inorganic minerals and other
particles. If sample are directly collected at the river bank or lakeshore, there is
possibility that especially microparticles will be unnoticed. The way of extraction

of all plastic particles from bulk environmental samples is a very crucial step.
To separate microplastics from sediments, different density gradient-based
separation methods can be used to separate from sediments (Hidalgo-Ruz et al.
2012). Microplastics due to their surface properties can fasten with any object to
which they make contact with. Initial methods of sample preparation and
plastic particles identification are lengthy and time consuming, so there is need
of extraction procedures optimization. Imhof et al. (2012) reported a novel method
for separation of plastic particles from sediments of aquatic environment and
developed a density separator named as Munich Plastic Sediment Separator
(MPSS) that can analyze a sample volume of up to 6 L in one run. Sediments
sample size should be reduced if high amount of organic matter and clay minerals
are present in it. For smaller sample volumes up to 250 ml, a MPSS could be
built. This density separator machine also provides an efficient recovery rate
of small microplastic particles (<1 mm in size) and is commercially available
(Imhof et al. 2012). However, other method reported by various authors, involves
the use of elutriation/fludization followed by density separation, were also found
to be efficient methods (Claessens et al. 2013; Nuelle et al. 2014) that can be tailored
to obtain maximum recovery of microplastics from diverse sediments types (biota-
rich sediments, sandy or clay soil, etc.). A variety of plastic particles obtained in
separation process depend on the density of solution used. In most of previous
studies related to marine or estuarine environments, sodium chloride was used
at the density of 1.2–1.5 kg/L for efficient recovery of most of commercially
produced plastics (Browne et al. 2011; Hidalgo-Ruz et al. 2012). Recently authors
suggested the use of zinc chloride (ZnCl2) or sodium iodide (NaI) at the density
of 1.6–1.7 kg/L as separation fluid (Claessens et al. 2013, Nuelle et al. 2014).
Both separation fluids are cheap, being easily recovered and can be used more
than once but exhibit moderate toxicityto biota. Use of nontoxic polytungstate
solution at the density of 2.0 kg/L as separation fluid is more costly method
(Zbyszewski and Corcoran 2011).
Segregation of Organic Matter
The removal of plastic particles from organic material like algae, shell fragments,
sea grasses, small organisms, etc. has been shown to be necessary for both
marine matrices and freshwater samples matrices. Continental ecosystems
including eutrophic lakes and streams are rich in organic matter and only
use of density separation process for plastic particles isolation natural organic debris
is not efficient method. Hence several oxidation agents such as strong nitric
acid, hydrogen peroxide, hydrochloric acid, and mixture of sulfuric acid
and hydrogen peroxide were used to exclude organic matter from different
environmental samples. However, treatment of strong acids or bases has to be
avoided because they influence on nature of plastic particles as the pH-sensitive
polymers partially degraded or dissolved (Imhof et al. 2013; Claessens et al. 2013;
Mathalon and Hill 2014). Therefore, there is need of exploration of alternative anti-
organic treatments. Recently a wet oxidizing method by utilizing density separation
technique followed by 15% hydrogen peroxide digestion has been reported by
Avio et al. (2015). Some polymers such as polyoxymethylene and polyamide are
affected by concentrated hydrogen peroxide (Claessens et al. 2013). Cole et al.
(2014) reported the enzymatic digestion of organic materials by using proteinase
K resulted as a consistent method to extract microplastic from zooplanktons samples.
But it is an expensive approach regarding larger organisms.
Identification and Characterization of Microplastics
Identification and quantification of plastic particles are very sensitive and crucial
steps to address the plastic contamination. Characterization of particles are
concerned with the morphological descriptions, color, shape, type, source, chemical
composition, and degradation stage of particles (Eerkes-Medrano et al. 2015).
The use of reliable identification technique is foremost important challenge.
Eriksson et al. (2013) investigated the elemental composition of particles that
were visibly identified as microplastics and reported that most of particles
that initially identified as microplastic were in actual aluminum silicates exhibiting
0.355–1.0 mm size. Themost consistent method for characterization of plastic
particles is infrared spectroscopy (IFTR) (Hidalgo-Ruz et al. 2012) and Raman
spectroscopy (Lechner et al. 2014) or for some polymers by the use of scanning
electron microscopy-energy dispersive X-ray spectrometry (SEM-EDS) (Rocha-
Santos and Duarte 2015) for the analysis of the chemical composition of micro-
plastics. After pyrolysis, gas chromatography and mass spectrometry (GC-MS)
can also be carried out, but information about particle shape and size is lost (Fries
et al. 2013; Nuelle et al. 2014).
Environmental and Health Effects of Microplastics
The presence of microplastics in freshwater ecosystems is highly significant

from environmental point of view around the world. Studies on freshwater
ecosystems reported that huge quantity of plastic litter have been recorded in both
aground sediments (mainly lakeshores and also river banks) and water samples
(primarily surface water of lakes and rivers) and finally introduced in to marine
ecosystems through rivers (Dris et al. 2015). There is need of consistent data
about huge ecological and biological risk causing polymers itself and its
associated chemicals in continental waters. In addition to direct interaction of
microplastic with organism, It also has wider impact on abiotic factors or exhibits
indirect effects on biotic communities (Bakir et al. 2014). Toxicity of microplastics
can also be associated with adsorbed substances like phthalates and BPA on
their surfaces (Lechner et al. 2014), or they can harm through physical
damage due to their shape (Mccormick et al. 2014). Indirect effects of
microplastics ingestion relates to reduced food consumption or intestinal

blockage leading to death. Moreover, environmental contaminants including
persistent organic pollutants (POPs) that are adsorbed by microplastic particles
also show hazardous biological effects (Yonkos et al. 2014).
Impact of Microplastics on Freshwater Biota
Various authors have been reported that freshwater biota have the ability to ingest
microplastics. Imhof et al. (2013) reported the microplastics ingestion in annelids
(Lumbriculus variegatus), crustaceans (D. magna and Gammarus pulex),
ostracods (Notodromas monacha), and gastropods (Potamopyrgus antipodarum).
They showed that there was 35% of exposed individuals exhibited microplastics
ingestion (Imhof et al. 2013). Freshwater gudgeon (Gobio gobio) collected
from 11 French streams showed that 12% microplastics accumulated in their
tissues (Sanchez et al. 2014). However, the rate of microplastics ingestion and
accumulation in various fish species will definitely depend upon their feeding
approaches. Another studies described that water flea Daphnia magna rapidly
ingests microplastics under laboratory-controlled conditions. (Rosenkranz et al.
2009). They found that microplastics of size 0.02–1 mm have the ability to
cross the gut epithelium and accumulate in fat storage droplets. To date
available data demonstrated that a spacious range of freshwater taxa is prone
to microplastic ingestion and toxicity effects remain uninvestigated for these
species. Rosenkranz et al. (2009) reported the accumulation and retention of
20–1000 nm microplastic particles in the freshwater water flea, Daphnia magna.
Von Moos et al. (2012) in his study on Mytillus edulis described about the
inflammatory response in the tissue and reduction in membrane stability within the
cells of the digestive system due to ingestion of microplastics (particle size
>0–80 mm). The particles having the size between 3.0 and 9.6 mm have the ability
to translocate from the digestive tract in the circulatory system of M.edulis where
they can persist for more than 48 days. Similarly, in water flea Daphnia, ingested
microplastic can cross the epithelial cells of digestive tract and accumulated in fat
storage droplets. Liver stress response and early tumor formation have been
observed in Japanese medaka fish (Oryzias latipes) due to bioaccumulation of
virgin polyethylene fragments (Rochman et al. 2013b).
In spite of direct physical impact from the microplastics itself, swallowed plastic
particles also exhibit chemical impact on organisms, and they behave like a sink
to deposit and transport chemicals including PBTs (persistent, bioaccumulative,
and toxic substances), for example, polychlorinated biphenyls (PCBs), or the
chemicals that are added during plastic production such as plasticizer (Teuten et al.
2007; Browne et al. 2008; Engler 2012). The potential of these two types of
chemicals to be transferred to biota is very low. However, there is availability of
limited knowledge about important contaminants like endocrine disrupting
compounds (EDCs), bisphenol A, and pharmaceuticals (Fries and Zarfl 2012;
Wagner et al. 2014). The presence of some well-renowned EDCs such as phthalates
on microplastics have been reported by Fries et al. (2013). Various other authors
described the leaching of EDCs from plastics (Wagner et al. 2014). Rochman et al.
(2013b) reported in their studies that translocation of hydrophobic contaminants
such as phenanthrene through sorption-desorption mechanism on microplastics to
organisms is carried out more easily as compared to other natural sediments.
Laboratory experiments that investigated on O. latipes demonstrated that fish
exposed to diet constituting microplastics with adsorbed chemicals bioaccumulated
in it exhibited severe signs of liver stress including depleting glycogen and
histopathological alterations in comparison to fish supplemented with only micro-
plastics without adsorbed chemicals (Rochman et al. 2013b). Oliveira et al. (2013)
investigated the exposure effect of microplastic with sorbed pyrene on freshwater
Pomatoschistus microps. They reported larger pyrene metabolite bioaccumulation
and toxic effects leading toward mortality as compared to fish exposed to
pyrene alone and no microplastics. Such kind of lab experiments will be helpful to
generate data regarding effect of microplastics to organisms under freshwater
conditions. However, its significance to test impacts under lab conditions and in
the field will be different because in natural environment, understanding of exposure
is still restricted.
Microplastics Toxicity to Aquatic Organisms
Various biological processes and functions of organisms are being affected by

plastic debris that enters in the water bodies from all sources, i.e., terrestrial as
well as aquatic environment (Webb et al. 2012). Microplastic consumption
shows highly negative effects on biological systems of freshwater biota (Table 2).
Few routes for microplastic uptake have been studied. Results indicated
the pivotal effects of microplastic ingestion on the uptake of nutrients and food
by the organisms. Most of the aquatic organisms ingest these particles along with
food particles that adhere to them or they adhere to it (Phillips et al. 1980).
Some organisms have been reported to ingest these particles or nutrient-deficient
particles intentionally in order to feed on biofilm microbial flora. The particles
are then excreted out (Au 2017). Consumption strategies and mechanisms have
been visualized and studied in various groups of invertebrates living in
different zones of water bodies including benthic and pelagic zones, such as
crustaceans (Murray and Cowie 2011), amphipods, barnacles, lugworms (Thompson
et al. 2004), sea cucumbers (Graham and Thompson 2009), and mussels (Browne
et al. 2008).
Effect on Energy Reserves and Growth
Mussels (Mytilus edulis) and clams (Atactodea striata) exposed to microplastics

(including nanoplastics of polystyrene nature) along with food show decreased
algae uptake by filtering ability and pseudofeces production. Since exposing
Table 2 Microplastics toxicity studies on freshwater biota (chronological descending order of last 5 years)
366
Authors Size
Taxa/species studies Polymer typea (μm) Concentration Time of study Pathological effects
Amphipod/Gammarus (Weber et al. PET fragments 10–150 0.8–4000 particles mL1 48 days No effect on behavior, growth, and
pulex 2018) metabolism
Fish/Danio rerio (Lei et al. PS,PA, PE, PP, 0.1, 1.0, 0.001–10.0 mgL 10 days Oxidative stress, intestinal damage,
2018) PVC and 5.0 low mortality
Amphipod/Hyallela (Au 2017) PE powder 10–27 PE (10) 10 days for LC50 of PE: 4.6 104 MPs/mL
azteca 0–105 P/ml acute exposure
PP fibers PP (10) LC50 of PP: 71.4 MPs/mL
0–90 P/ml
PE (42) 42 days for Non dose-dependent effect when conc.
02 104 P/ml chronic Increased from 10.000
exposure Decreased reproduction
Fish/Pimephales (Au 2017) PE 10–27 0–10,000 MPs/ml 4 days for acute Dose-dependent ingestion
promelas exposure No significant mortality
Reproductive effects not quantified
Fish/Danio rerio (Lu et al. PS beads 0.07–5.0 20–2000 μg/ml 21 days Inflammation and lipid accumulation in
2016) liver
Fish/Carassius auratus (Grigorakis PE microbeads 50–500 50 particles per pellet of 6 days No accumulation in fish gut
(Goldfish) et al. 2017) & microfibers food having size 3 mm No mortality
Cladocera/Daphnia (Rehse et al. PE beads 1–4 12.5–400 mg/L 96 h 1.0 μm: LC50 is 57.43 mg/L
magna 2016) 90–106
Cladocera/Daphnia (Ogonowski Primary MPs 1–5 102–105 particle/ml 21 days Primary MPs: no effect
magna et al. 2016) Secondary MPs 2.6 1.8 Secondary MPs: high mortality
Kaolin 4.4 1.1 Kaolin: no effect
Osteichthyes/Clarias (Karami et al. LDPE <60 50–500 μg/L 96 h Significant alterations in metabolism
gariepinus (bony fish) 2016) (fragments) 10–100 μg/L
PHE
Osteichthyes/Oryzias (Rochman LDPE <500 8 mg P/ml 60 days Sign of stress in liver, glycogen
latipes et al. 2013b) (fragments) depletion, single-cell necrosis
Osteichthyes/ (Oliveira PE beads+ 1–5 MP: 18.4–184 μg/L 96 h Microplastic delayed pyrene induced
Pomatoschistus microps et al. 2013) Pyrene Pyrene: 20–200 μg/L mortality, reduced AchE activity
a
M. Shafiq et al.
Polyamides (PA), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), phenanthrene (PHE), and polyethylene (PET)
time duration was kept 8 h and repeated for only 10 days, the effects for longer and
chronic duration are unknown. Estimated effects are depleted energy level (due to
starvation) and low food consumption (Wegner et al. 2012; Xu et al. 2017). Energy
depletion and reduced algae consumption, due to microplastics (mainly polystyrene)
consumption, have been depicted in copepods (Calamus helgolandicus) (Cole and
Galloway 2015). Microplastics along with food cause reduction in prey-predator
activity in juvenile goby (Pomatoschistus microps) obtained from river called Lima.
Interestingly, the consumption efficiency of Artemia was not significantly affected in
juvenile gobies collected from Minho River, a nearby estuary, suggesting that there
may also be other factors influencingorganism susceptibility that are water body-
specific (De Sá et al. 2015). Body sizes among crustaceans (D. magna) and Hyalella
have been observed to be reduced when they were exposed to polystyrene and
polyethylene, respectively (Besseling et al. 2014). The safe limit for microplastic
ingestion along with food material is yet to be determined. It was observed that with
low concentration of algae along with microplastics, growth in the organisms
lowered as compared to along with high-algae concentration, i.e., 9 μg C/ml versus
0.4 μg C/ml. On the other side, 1 102–105 microplastics per ml were
used. Results suggest that in order to maintain normal growth, diet should contain
more food than usual to counter act the drastic effects of microplastics (Ogonowski
et al. 2016). Microplastics get deposit on surface of algae thus stopping
light penetration and ultimately photosynthesis. Decrease in photosynthesis
also lowers the growth rate due to blocking of light, CO2, and O2 (Zhang et al.
2017). Polystyrenes also effect the algal growth in the same manner (Besseling et al.
2014; Sjollema et al. 2016). Pacific oysters were exposed with 2–6 μm polystyrene
microplastics for 2 months. Results indicated an increase in algal consumption,
which explains that, for compensating the rate of microplastic ingestion,
algal consumption was increased (Au 2017). It has been observed that if there are
enough nutrients and food availability, then the exposure to microplastics do
not affect the growth of organism. Statistical analysis of microplastic exposure
to mussels and lugworm (both having different modes of nutrition, i.e., filter
feeding and deposit feeding, respectively) and its effect on the total energy of the
cell depicts no overall change in the energy distribution in both organism with
the increasing microplastic concentration as well as consumption of energy (Van
Cauwenberghe et al. 2013). It is evident from investigations that stress is related
to the increase in respiration (energy intake) and results in the distribution of
energy, which is shifted in such a way that it is preferred for the survival and growth
of organism instead of reproduction requirements (Ogonowski et al. 2016;
Sussarellu et al. 2016).
Exposure of 500 20 μm sized microplastic fibers for 14 days on amphipods
collected from freshwater resulted in the reduced food intake (mainly leaf material)
although the fiber from food material required 16 h for removal (Blarer and
Burkhardt-Holm 2016). Similar is the case with juvenile H.azteca, when it
was exposed to microplastics for 10 days duration, reduction in growth rate was
noted (Au 2017). Daphnia magna was also studied for the effect of microplastics
on nutritional uptake, and results depicted a decline in food uptake. Both primary
and secondary microplastics were used (Ogonowski et al. 2016). Although

the reason of decrease in assimilation of food by the exposed organism to
microplastics is not understood completely, chances of destruction of gastrointestinal
tissues are present which results in poor rate of food intake (Blarer and Burkhardt-
Holm 2016).
Inflammation due to microplastics in mussels, M. edulis and A.marina were
observed by various scientists (Von Moos et al. 2012; Wright et al. 2013). Since in
lugworms due to microplastic’s inflammation along with long residence time
indigestive tract cause the reduction in food intake, it ultimately results in the
depletion of lipid energy stores of the body (Wright et al. 2013).
Effect on Reproduction
Investigation about the effects of microplastics indicates that among

microplastics, polyethylene and polystyrene caused reduction in the production
of newborns in a number of species, i.e., C. helgolandicus, H. azteca, and
D. magna (Cole and Galloway 2015; Ogonowski et al. 2016). Reduction in
body size, small number of eggs production, and other malformations were
observed in the bodies of a plankton (Daphnia magna) when they were exposed to
nanoplastics of polystyrene nature (Besseling et al. 2014). Fertility and reproduction
efficiency was also affected and reduced in the Ostreidae species upon exposure
to polystyrene microplastics. Moreover, their larvae development was also
affected due to decrease in the production (by 38%) and size of oocytes (by 5%).
Movement speed of sperms was also observed to be reduced (by 23%) which
contributed in the reduction in development efficiency (Sussarellu et al. 2016).
Observation of nauplius production, after the exposure of polystyrene micro-
plastics particles of 0.005–0.5 μm size, depicted the reduction in the conversion of
larva (Lee et al. 2013) to adult Ostreidae via copepodities. T. japonicus also
showed decrease in the production of larvae over two generations. The energy of
the body is also used for survival and respiration instead of reproduction due
to microplastic ingestion (Sussarellu et al. 2016; Au 2017). Apart from the
harmful effects of microplastics, they can be beneficial for the survival and traveling
of eggs of organisms over long distances as microplastics are not degradable
easily. Moreover, the danger of predators for eggs is greatly reduced. Oocytes and
spermatozoa of snails experience damage to their structures due to the exposure
to paint residues in the form of chips. Main compounds present in them are
polyurethane, polyethylene, expanded polystyrol, and polyethylene terephthalate
(Watermann et al. 2017). Microplastics alone are not responsible for the destruction
or harm caused to the reproductive system, but the presence of other contaminants
on it is also responsible. Among these contaminants are those that cause
anatomical and physiological disruptions to the endocrine system. For example,
tributyltin, various metals, and diuron are some of the contaminants (Watermann
et al. 2017). The exposure of Japanese rice fish to contaminants (causing endocrine
disruption) which leached from polyethylene microplastics severely resulted in
the toxicity of reproduction system (Rochman et al. 2014a). Genes expression is

regulated to a small extend as well. Japanese rice fish showed lowered production of
estrogen receptor genes, choriogenin H, and vitellogenin genes, when exposed to
polyethylene microplastics (Rochman et al. 2014a). Microplastics effect on the
developmental system of the organisms lead to serious problems in the food
web and environmental balance of predator-prey ratio. Virgin polyethylene micro-
plastics pose less abnormalities in juvenile brown mussels as compared to aged
microplastics (Au 2017).
Bioavailability of Additives and Adsorbed Environmental

Contaminants
The origin of microplastics is not restricted; it can be added to the environment

through industries or other processes in which they are produced as a byproduct
(Rochman et al. 2013b). A number of other chemicals are associated with micro-
plastics. These include organic and inorganic contaminants. Among inorganic
contaminants are barium, silver, zinc, titanium dioxide nanoparticles, and sulfur
(Fries et al. 2013; Kang et al. 2015). Among organic contaminants, perflouroocta-
nesulfonate, polycyclic aromatic hydrocarbons, dichlorodiphenyltrichloroethanes,
perfluorooctanesulfonamide, and polychlorinated biphenyls are also present
(Rochman et al. 2013b; Au 2017). The presence of microbeads (taken from
cosmetic products) resulted in the sorption of cadmium from contaminated
intertidal sediment and decreased the amount of cadmium in pore and surface
water (Boucher et al. 2016).
Hormonal control is observed to be greatly affected by other chemicals like
pthalates and some of the plastic additives like nonylphenol, bisphenol A, and
plastic monomer, i.e., styrene (Iguchi et al. 2005; Fent et al. 2014). Contaminants
may or may not be absorbed from the soil through microplastics as it has been
calculated from the data gathered through analysis that there is no correspondence
between the microplastics amount collected and concentration of contaminants
infield organisms (Paul-Pont et al. 2016). Growth of biofilms on microplastics
may cause the differences in contaminants absorption. The presence of organic
contaminants indicates that biofilm is present in higher amount on microplastics
(Au 2017).
From the data obtained from various studies, it is observed that contaminants
attached to the microplastics affect the organism’s biological pathways (Oliveira
et al. 2013; Rochman et al. 2014a; Avio et al. 2015). The ways in which
contaminants along with microplastics are taken or absorbed contribute to their
bioavailability. From thermodynamic models, it has been suggested that
contaminants present on the surface of microplastics (in high concentrations)
are transferred to the organisms, and this transfer is favored kinetically.
So microplastics are not a significant factor for contaminants (Koelmans et al.
2016). Exposures of polyvinyl chloride microplastics in the presence of phenan-
threne or 17α-ethinylestradiol (EE2) to larval zebrafish resulted in greater sorption
of EE2 on microplastics despite phenanthrene having a higher logKOW,

suggesting that contaminant bioavailability in the presence of microplastics cannot
be predicted using physiochemical properties alone (Sleight et al. 2017).
There is need to have advanced techniques as well as equipment for laboratory
so that it can be detected that whether microplastics have any effect on the absor-
bance of contaminants from environment in the organisms. Small size of plastic
debris may play a great role in the availability of contaminants. This is due to two
reasons, i.e., small size and floating capacity of microplastics that make
them readily available for the pollutants thus allowing them to move to greater
distances. Equilibrium is reached at a lower rate by the microplastics of smaller size
to that of water. This is due to their large surface area (Au 2017). Since urban areas
discharge a large amount of pollutants, so the addition or presence of microplastics
in these water bodies increases the amount and time for contaminants degradation.
The time required to reach equilibrium for these contaminants to water is
also reduced to a great extent. Organisms and food web exposed to such
environment tare greatly affected by the contaminants adhered to the microplastics
(Karapanagioti et al. 2010).
Exposure of polyethylene microplastics (1–5 μm) contaminated with pyrene on
goby fish for 96 h caused changes in the swimming movement: increase in
the amount of bile metabolites like pyrene and decrease in activity of certain
enzymes. These enzymes are acetyl cholinesterase (Obbard et al. 2014) and
isocitrate dehydrogenase (IDH) (Oliveira et al. 2013). Abovementioned enzymes
are important in cellular regulation and are involved in various pathways.
For example, acetylcholinesterase involves in neurotransmission of fish and
aerobic respiration as well as an antioxidant defense of a cell control by isocitrate
dehydrogenase enzyme (Oliveira et al. 2013). Changes in swimming behavior and
decrease in antioxidant defense, due to less secretion of AchE, it becomes difficult
for the organism to fit in the environment. When Oryzias latipes was exposed
to field-aged polyethylene microplastics as compared to virgin polyethylene micro-
plastics, high concentration of polychlorinated biphenyl 28 (PCB28), PAH chrysene,
and polybrominateddiphenyl ethers (PBDEs) were observed (Rochman et al.
2014b). In spite of degradation pathways that alter the physical and chemical
properties of microplastics, aged microplastics may act as major environmental
contaminants (Au 2017).
Trophic Transfer of Microplastics
The presence of microplastics in the excreta and worn out tissues of organisms
of higher trophic levels indicate that potential for trophic transfer is present which
occurs along with the ingestion of microplastics. However, very little research
data is available for this transfer (Eriksson and Burton 2003; Lusher et al. 2017).
Since microplastics are very small in size, they are often ingested by the small
organisms and are transferred to organisms at higher trophic levels when they
feed on small organisms (Desforges et al. 2015). Imhof et al. (2013) carried out
freshwater research on ingestion of microplastic by invertebrates revealed that

animals residing at various trophic levels exhibit the interaction and ingestion of
microplastic. Various microbial communities dwelling at most basic organismal
level such as autotrophs, heterotrophs predators, and symbionts interact with
microplastics (Zettler et al. 2013). Similarly sea birds residing at higher trophic
levels ingest microplastics directly as well as through fish indirectly (Tanaka et al.
2013). Fur seals and sea lions living in subantarctic islands having ingestion
of microplastics showed the level of penetration of microplastics in food web of
remote locations (Mcmahon et al. 1999; Eriksson and Burton 2003). These higher
animals most probably get microplastics on ingestion of fish. Even 1 mm plastic
fragments were identified in sea lion scats given the evidence coming from fish
Electona subaspera (Mcmahon et al. 1999). Average concentration factor of
microplastics in fish is 1–1.9 pieces per fish whereas in seals this factor increases
from 22 to 160 times. This is may be due to direct and indirect ingestion of
microplastics in higher trophic level. However, freshwater birds and storage
gizzards may ingested the microplastics (Dris et al. 2015). Recently, Au (2017)
conducted lab studies related to trophic transfer of fluroanthene (FLU) contaminated
microplastic particles from exposed amphipods and copepods to fathead minnows
and mummichogs. Further, about 1.3 mg fluroanthene was found in the bile of
hybrid striped bass that has eaten fathead minnows that were pre-exposed to
FLU-contaminated microplastic.
Legal Framework for Microplastics
Policy management related to microplastic pollution in freshwater bodies, in

comparison to marine water, is still at its infant stages. Policy programs to control
plastic debris freshwater aim (1) to understand the source, presence, and impact of
microplastic and (2) reduce or prevent further entrance of microplastic in the
environment. Policy initiatives could benefit from IMDCC and MSFD protocols to
establish regulatory activities for fresh waters. IMDCC (US Interagency Marine
Debris Coordinating Committee) controls the marine debris activities both at
national and international level as well as suggest research priorities, educational
plans, and regulatory activities (Rochman et al. 2013a). The European Commission
MSFD (Marine Strategy Framework Directive) has specified a technical
committee that identifies and recommends the research needs, implementation of
monitoring protocols, preventing debris inputs, and reduction of marine litter.
The MSFD debris description comprises the microplastics pollution and limitation
of its sources, accumulation, environmental effects including both physical and
chemical impacts, and chronological and spatial patterns (Galgani et al. 2013).
On the basis of previous research, it was noted that microplastic sized particles
<5 mm were found in US LA basin river fresh water abundantly, but their size range
are not subject to regulation (Moore et al. 2011). Another study was conducted in
the distant Lake Hovsgol of Mongolia reported that high level of microplastic
pollution in this lake, characterized by fragments of domestic origin, resulted

from absence of appropriate waste management system (Free et al. 2014).
The United Nations General Assembly approved the resolution, “Transforming
Our World: The 2030 Agenda for Sustainable Development” on 25 September 2015.
This resolution addressed with 17 renewable development goals with 169 allied
targets. Some of important points included in this agenda are to establish
eco-friendly waste management system for chemicals and all other wastes including
plastic waste too, in accordance to international standards and considerably
reduce their discharge in soil, water, and air so that to minimize their hazardous
effects on human health and the environment (Brennholt et al. 2018).
The Group of 7 (G7) includes the seven developed countries (the USA, the UK,
France, Japan, Germany, Italy, and Canada). All G7 countries are much concerned
about environmental issues like climate change, sustainable development, plastic
pollution of aquatic ecosystems (both marine and fresh water), and nuclear
safety (Brennholt et al. 2018).
In 2015, the World Bank established a Pollution Management and Environmental
Health (PMEH) program that covers technical assistance and finance for
reducing pollution and improving health for all. Similarly in 2015, US government
passed Microbead-Free Waters Act, amending the Federal Food, Drug, and
Cosmetic Act that prohibits “The manufacture or the introduction or delivery for
introduction into interstate commerce of a rinse-off cosmetic that contains
intentionally-added plastic microbeads.” Here a plastic microbead is defined as
“any solid plastic particle that is less than five millimeters in size and is intended
to be used to exfoliate or cleanse the human body or any part thereof” (including
toothpaste). In this act, the term “microbead” is clearly defined to as primary
microplastics and also gives regulations to tackle the pollution of freshwater
systems (Brennholt et al. 2018).
Future Considerations and Conclusion
In the future, the release of microplastics in the environment as contaminants will

be amplified due to tremendous increase in world populations (predicted to
about double in next 40 years) (Browne 2015). Up till now, the main ambiguity
had been the lack of knowledge about the pollution caused by microplastics,
their source, and its concentration in environments. A lot of study has been done
on the microplastics presence in freshwater systems. But its ecological effects on
the water systems are yet to be related. The data on amount of microplastics
entering the waste management systems has been calculated in enough magnitude
as compared to quantity of microplastics entering the streams and other water
bodies. In order to know the particular behavior as well as the fate of microplastics,
nanomaterial research is very important. Progress in microplastics research can be
done only when the exact nature and type of microplastics is known, before they
are collected, analyzed, and processed in order to reduce the contamination due
to their production. There is dire need to do work on reduction and elimination of
sources and pathways of microplastic through (a) establishing and controlling

the inventory of material, (b) redesign the products by altering their process of
production to reduce the hazardous substances, and (c) using of novel equipments
and technologies to reduce the emission of microplastic in environment.
This chapter also gives the knowledge about the presence of toxic
bioaccumulative chemicals found on microplastics. Specie-specific relation exists
between the toxicity associated with adsorbed contaminants on microplastics and
species ingesting them. Most toxic microplastics are those that are polypropylene
in nature as compared to polyethylene. Swimming behavior has been disrupted in
the aquatic organisms due to microplastics ingestion. Polyethylene exposure to
organisms resulted in reduction in growth rates. Reproduction rates were not
affected greatly but occurred as a secondary factor for reduced growth.
Mortality can also be occurred due to microplastics ingestion. Microplastics
are transferred to higher trophic levels when one organism feed on the other which
has ingested those microplastics. The understanding about the microplastics is
developing rapidly, but the gaps are still present in the available knowledge
about microplastics.
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Impact of Material Chemistry on the
Performance characteristics of a Coal 16
Handling Plant
Kumar Harshit, Syed Ali Hussain Jafri, and Pallav Gupta
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
Centrifugal Pump . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
Different Types of Pumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
Comminution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
Beneficiation (Coarse Circuit) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
Beneficiation (Fines Circuit) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
Site Details of Pumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
Life Cycle of Warman Pump (Primary Pump) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
Graph of Head Versus Flow Rate for Two Distinct Pumps (171 and 172) . . . . . . . . . . . . . . . . 397
Life Cycle of a Warman Pump (Secondary Pump) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
Graph of Head Versus Flow Rate for Secondary Pumps 167 and 168 . . . . . . . . . . . . . . . . . . . . . 400
Life Cycle of Warman Pump (Over-Dense Pump) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
Graph of Head Versus Flow Rate for Over-Dense Pump 165 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
Curves of Other Horizontal Pumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
Other Horizontal Pumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
Performance Curve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
Abstract
The handling tasks at a coal beneficiation plant enhance the preparation of coal
by improving the techniques involved in each process and the various associated
parameters. The various kinds of equipment available at the plant increase the
K. Harshit · P. Gupta (*)

Department of Mechanical Engineering, A.S.E.T., Amity University, Noida, Uttar Pradesh, India
e-mail: pgupta7@amity.edu
S. A. H. Jafri
Department of Mechanical Engineering, Integral University, Lucknow, Uttar Pradesh, India

https://doi.org/10.1007/978-3-319-73645-7_173
380 K. Harshit et al.
efficiency of the respective machines and improve the quality of the product
derived from the plant operations. Economical storage, loading and unloading of
coal cars, maintenance of machines, and the improving technical knowledge
associated with each job depend completely on the handling equipment and the
management of the plant. In the present chapter, a complete assessment of the
coal beneficiation plant is presented in detail, with the four major parameters:
pumps installed, processes involved, material chemistry, and performance indi-
cators. These four parameters have major roles in the production of coal at the
respective plants, so it is crucial that the production and manufacturing firms
focus their major interests on these points. The text emphasizes the types of
processes and operations involved at the beneficiation plant as well as the
handling characteristics. The separation of coal into different segments is sig-
nificant for production as this increases the economic aspects for the respective
firms. Handling of the coal is an essential function in the industry because it
ensures the proper channelling of the coal to operations in different branches of
the plant, such as the thermal power plant and power house. These results and the
other parameters discussed in the chapter concern the impact of material chem-
istry on the performance of the plant’s machinery along with the various features
of machines such as pumps, allowing us to analyze the role of all the elements
involved during the separation of coal. The approach of this chapter is focused
on detailed study of the pumps, that is, the centrifugal pumps installed at the
washery plant, as they are the most basic elements for proper and efficient
operation. The chapter also provides various mathematical relationships, tabular
representations, and graphical approaches to aid the reader in understanding the
major parameters.
Keywords
Beneficiation · Material chemistry · Efficiency · Industries · Performance
Introduction
The combustible black sediment found in the layers of rock strata is termed coal.
This natural nonrenewable resource has an essential role in the production industry
as it is the premium source for the generation of electricity, and for this reason it is
exported throughout the globe for various purposes. Coal is composed primarily of
carbon, with other elements including hydrogen, nitrogen, and oxygen. In the class
of material application, coal is one of the most important natural resources along
with petroleum, as these run parallel when considering the economic condition of
any of the countries (Krevelen 1961).
Progress in technology allows using the techniques in any aspect of production in
a very sophisticated manner, so that the associated complex problems can be solved
readily and easily. The presence of coal is a gift of nature to a particular locale, but its
utilization techniques are the most important consideration (Krevelen 1961).
16 Impact of Material Chemistry on the Performance characteristics of a. . . 381
Automation of coal production nowadays is crucial for the steel industry as well as
mining areas (Ji-ping 2010a). Covered here is the complete automation of coal
production from its extraction from the mines to the processing zone, where it is
separated into different segments – clean coal, middling coal, and rejection coal –
and finally is made ready for transportation. On the basis of this presentation, it can
be assumed that efficient handling of this resource by automation should be taken on
serious grounds by any of the industries. Research efforts across the globe on
improving automation techniques are determining optimal solutions for many
aspects of production. In the coal industry, advanced techniques are being
implemented with various upgraded machine tools for proper technological appli-
cation. Because technological advances are contributing to many firms, we can say
that organizations should give more attention and investment of resources to these
technical aspects (Ji-ping 2010b).
The major segment of this chapter is focused towards the application of the
pumps established at the TISCO plant, as a case study, for the production of coal
in three categories: clean coal, middling, and rejection. The pumps installed at the
plant are of various types, but the present chapter is concerned with centrifugal
pumps. Pumps have an essential role in industry, with various associated applica-
tions during many operations (Stepanoff 1948). Pumps are located at almost all the
regions of the coal plant, depending upon the type of operation at the respective zone
(Moser and Schnitzer 1985). Pumps have a significant role in all aspects of the
industry depending upon the operation involved in separation of the coal into
segments (Lazzarin 1995). A washery plant has different units overseeing the
pumps on the basis of their type and operation, which aid in identifying problems
and rectifying these efficiently (da Costa Bortoni et al. 2008). The performance
curves presented in this chapter help in analyzing the relationship between various
pump parameters during operations in a beneficiation plant. Detailed study of the
pumping system is discussed along with all possible parameters to be considered in
the respective segments (Srinivasan 2008).
The context of the chapter is also aimed at describing the types of process
involved at the plant in handling and separating the coal. The process is divided
on the basis of the operations used during separation (Wheelock and Markuszewski
1984). Separation corresponds to the middling and rejection processes, which are
analogous; these have certain features differentiating the coal on the basis of size
and density of the material produced (Gan et al. 1972). Distinctive processes take
place during particular operations, such as comminution and beneficiation
(Nadkarni and Williams 1983). The beneficiation plant is completely focused on
the preparation of coal from the raw material through a simple crushing operation
(Krevelen 1961). This process involves complex circuit methods for cleaning
purposes, covering each and every size of coal, that reject all the impurities linked
with the run of the mine (ROM) materials (Akbarnezhad et al. 2011). These
different methods are the key in coal preparation, in which gravity separation is
significant in the segmentation of raw coal having different sizes, densities, etc., by
the use of equipment such as cyclones. The froth floatation method is a dominant
coal cleaning method for fine-sized particles (Gan et al. 1972). The beneficiation
plant is used for the preparation of coal in which impure coal is made into clean
coal, plus middling and rejection, depending on the market demand. The main
agenda of this industry, which is taken as a case study, is to produce the maximum
amount of clean coal having a minimum ash content. The other content obtained
from the raw coal apart from clean coal also has certain functions: rejection coal is
used in the production of electricity whereas middling is used by the company itself
for various purposes (Yoshiie et al. 2012).
The chapter is also an attempt to understand the three main factors of the coal
beneficiation plant: the performance characteristics of the machines installed, the
role of the machines (pumps), and processing technologies. Performance charac-
teristics have been plotted on the basis of data collected by the pumps during
operation, and these data help in establishing a framework regarding the different
parameters associated with pumps (Stepanoff 1948). Along with the production and
handling of coal, the coal plant is also focused on the safety of the environment
(Carley 2009).
Centrifugal Pump
A turbo-machinery device is used for transportation of fluid by converting the flow

of fluid from rotational energy into hydrodynamic energy. Fluid strikes the motor,
which allows the impeller to rotate, thus resulting in the rise of water, leading to the
development of mechanical energy. The rotating axis allows the entry of fluid, which
is finally carried away through an exit (Croba and Kueny 1996). The context here is
focused on the study of centrifugal pumps and their applications in the separation
and handling of coal (Lobanoff and Ross 2013).
Basic formulae to be incorporated for calculation:
Solving for water horsepower
WHP ¼ Q H=3960
Water Horsepower
WHP = Q*H/3960 Solve for water horsepower
Q = 3960*WHP/H Solve for flow rate or discharge
H = 3960*WHP/Q Solve for total head
N = WHP/BHP Solve for pump efficiency
BHP = 100*Q*H/3960n Solve for brake horsepower
where WHP = water horsepower; Q = flow rate or discharge; H = total head;

n = pump efficiency; and BHP = brake horsepower.
Different Types of Pumps
Primary Pump
The role of the primary pump is to deliver the overflow of clean coal, consisting of
fine particles (Gan et al. 1972). This flow is supplied to the primary distribution box,
from which it is finally carried over to the cyclones, where it is again distributed on
the basis of density (Gan et al. 1972). Density of the substance is modified by mixing
or adding media used for gravity separation, and then finally, by means of a conveyor
belt, the coal is carried to the desired tank location. These pumps work in pairs, and
the pairs work alternately depending upon the requirement (Fig. 1).
The unit numbers are 170, 171, 172, and 173.
Secondary Pump
The secondary pump has a function similar to that of the primary pump. It is used for
carrying particles to the secondary distribution box located at the 25-m height block.
The coal is then carried forward towards the secondary cyclones that are used to
separate the middling and rejection quantities (Gan et al. 1972). Finally, with the
conveyor belt of these particles, coal is carried to the rejection and middling tanks
(Yoshiie et al. 2012).
The unit numbers are 166, 167, 168, and 169.
Over-Dense Pump
A high-density solid constitutes the mixtures of solids and liquids having various
characteristics including both physical and chemical parameters. The over-dense
pump has a significant function in the transportation of high-density solids during the
separation process. Substances having a high proportion of solids, such as sewage
sludge, waste sludge, and bituminous coal sludge, are carried to distant locations in
the beneficiation plant (Nadkarni and Williams 1983). These conveying distances
are made possible by bridging with a high-density pump or mechanical conveying
equipment (Fig. 2).
The unit numbers are 164 and 165.
Fig. 1 Primary pump setup at

plant
Fig. 2 Over-dense pump

setup at plant
Fig. 3 Dilute pump setup at

plant
Dilute Pump
The dilute pump is also important in delivering the working constituents to desired
locations along the conveyor belts (Ji-ping 2010a). Figure 3 presents a pictorial
representation of the dilute pump at the coal beneficiation plant, with specific unit
numbers associated with each pump. Unit numbers help in recognizing the location
of the pump as well as other machines as it is a little difficult task to locate the pumps
without numbers.
Thickening Pump
Underflow slurries of particles sized from 5 mm to 13 mm are carried out during the
operations at the beneficiation plant (Nadkarni and Williams 1983). Various concen-
trated slurry mixtures containing abrasive particles have a high-grade nickel con-
centrate, a mixture of copper and nickel, or a copper slurry with low nickel content,
with flows up to 359 l/min (95 US GPM), and up to 72% solids density of 4.29–4.97
(Krevelen 1961). Depending upon demand and operating conditions, the soft rubber
lined (SRL) centrifugal pump has been replaced by the VF80s pump (Ji-ping 2010a).
Various parameters are changed in these pumps: air domes of approximately 80 l
have been set up at the discharge line to control the pulsating rate caused by the
slurries, and expansion bellows are installed at the suction side to improve the
suction condition (Lazzarin 1995) (Fig. 4).
Fig. 4 Thickening pump
Froth Floatation Pump

The froth pump is essential in the separation of rich minerals from gangue during
mineral processing (Yoshiie et al. 2012). In this process air is added, and rich
minerals are trapped in the air bubbles and finally rise to the top of the floatation
cell tank, allowing the waste particles such as clay, etc., that have no further use, to
settle at the bottom of the cell (Gan et al. 1972). Different processes such as
scavenging and cleaning are carried out inside the floatation tank (Ji-ping 2010a).
The floatation pump also has a significant role in extraction plants for oils and
other resources where froth is used for the removal of bitumen and other undesirable
substances (Lazzarin 1995). As it is difficult to move oils at low speed and temper-
atures, a change is made in the pump speed depending on the operational demands
(Moser and Schnitzer 1985). Changes in pump speed also lead to the development of
friction from self-lubrication of fluid where water separates and forms different
lubricating layers (Stepanoff 1948). When water or any working fluid enters the
pump, different operations take place, low pressure is developed at the impeller, and
pre-rotation produces the centrifugal force that allows the slurries to settle and air to
rest at the center (Moser and Schnitzer 1985). According to Abulnaga (2004), the
pump may use (a) a large eye diameter, (b) an inducer or extension of the impeller
vanes into the suction pipe, (c) a recirculating pipe from the discharge side of the
pump with pressurized froth to break up the bubbles at the eye, (d) tandem vanes at
the impeller shroud, (e) split or secondary vanes at the shroud, or (f) a vertical
arrangement; hence, the split vane should be thick enough to resist the wear (Fig. 5).
Unit numbers are 175 and 176.
Vertical Sump Pump

Vertical sump pumps are intended for use in industrial pumping applications to pump
clean or lightly contaminated liquids, fibrous slurries, and liquids containing large
solids from the deep sumps (Croba and Kueny 1996; Lobanoff and Ross 2013). The
pumping head is suspended into the pumped liquids and the drive motor is dry
installed on the top. The pump has a separate discharge pipe and support pipe
column (Lazzarin 1995). The vertical sump pump has a vertical line shaft with
slide bearings or a cantilever design without slide bearings (Ji-ping 2010a). A
vertical sump pump at the coal plant is shown in this figure (Fig. 6).
Unit numbers are 304A and 304B.
Fig. 5 Froth floatation Pump
Fig. 6 Vertical sump pump

setup at plant
Effluent Pump
The effluent pump is used to handle semi-solids and to pump filtered effluent to leach
fields from the septic tank in the beneficiation plant (Nadkarni and Williams 1983).
These pumps are crucial in segmentation of coal when are used as sump pumps and
sometimes become clogged by some thick liquid, or grass or debris, etc. (Stepanoff
1948). Separation of semi-solids from raw coal is efficiently handled by the effluent
pump, and thus the plant can produce a high quality of clean coal with complete
purity (Srinivasan 2008) (Fig. 7).
Unit numbers are 111 and 112.
Processes
The present chapter discusses the various operations associated with the handling of
coal at a beneficiation plant (Sanders 2007). The coal beneficiation plant has a
capacity of 600 tonnes per hour; it has a control room handling all the plant
operations. As not much reduction in size of the feed is required for a coal
beneficiation plant, a de-shelling plant is needed (Gan et al. 1972; Carley 2009).
As there is no grinding plant, the dewatering section is present at a lower height than
Fig. 7 Effluent pump

installed at washery #2
the main beneficiation plant so as to optimize the cost associated with the pump. A
filtration section is present at the beneficiation plant for the dewatering of fine coal.
The various processes involved in the coal beneficiation plant depend upon the types
of equipment used there and are categorized in various forms.
Comminution
Comminution is the reduction of solid materials of one average particle size to a

smaller average particle size by crushing, grinding, cutting, vibrating, or other
processes (Gan et al. 1972). In geology, it occurs naturally during faulting in the
upper part of the Earth’s crust. In industry, it is an important unit operation in mineral
processing, ceramics, electronics, and other fields, accomplished with many types of
mill (Moser and Schnitzer 1985). In dentistry, it is the result of mastication of food.
In general medicine, it is one of the most traumatic forms of bone fracture (Lazzarin
1995)
Equipment used:
• Banana screen
Its distinctive shape gave the multi-sloped screen the name “banana.” In industry,
the “banana” term is used interchangeably with the term “multi-sloped.” Used in
wet and dry applications, banana screens are vibratory equipment that uses the
distinctive shape for inclined horizontal screens, which as the name implies are
horizontal and do not have the banana shape (Ji-ping 2010a). Improper screening
means that a large amount of fines will remain with the oversized material (Gan
et al. 1972; Carley 2009). The result is high recirculation volumes and greater
wear of downstream process equipment. Being multi-slope, the screens offer
higher screening capacity, as mentioned earlier (Ji-ping 2010b). They also are
good for recovery in feeds with a very high percentage of near-sized material
(Gan et al. 1972).
The banana screens used at CHP were from Metso, their aperture size was
113 mm, and dry screening was done; these screens were used to perform closed
circuit crushing.
Specifications of banana screen:

• Single deck
• Width, 1800 mm
• Length, 4800 mm
• Tonne per hour (tph), 120–125
• Motor, 15 kv
• Speed, 1500 rpm
• Equipment numbers: 178, 179, 180, 181, 182, 183, 184, 185
Specifications of clean coal screen:
• Single deck
• Capacity, 80 tph
• Feed size, 13 mm–0.5 mm
• Equipment numbers: 156, 157, 162, 163
Specifications of middling screen:
• Capacity, 60 tph
• Size, 13 mm–0.5 mm
• Model number, T11
Specification of middling and rejection screen:
• Capacity, 80 tph (Fig. 8)
• Roll Crushers
A simple standard roll crusher consists of two horizontal cylinders that revolve
toward each other. The set of roll crushers is determined by shims, which cause the
spring-loaded roll to be held back from the solidly mounted roll (Ji-ping 2010a).
The main advantage with roll crushing is that lesser fines are produced; for this
Fig. 8 Banana screen

installation at Washery #2
reason crushing is used for coal crushing as the processing cost of fines is higher
than that of coarse particles (Stepanoff 1948). Roll crushers are very useful in
handling friable, sticky, frozen, and less abrasive feeds, such as limestone, chalk,
coal, gypsum, phosphate, and soft iron ores (Srinivasan 2008). The rolls may be
gear driven but this limits the distance adjustment between the rolls, and modern
rolls are driven by a V-belt from different motors (Ji-ping 2010b; Lobanoff and
Ross 2013). The great disadvantage of the roller crusher is that large rolls are
required in relationship to the size of the feed particles so as to achieve a reasonable
ratio and also require a large amount of capital (Gan et al. 1972; Yoshiie et al. 2012).
• Impact Crushers
The impact crusher is used for coarser crushing. In this crusher, material falls
tangentially on to a rotor running at a speed of 250–300 rpm, receiving a glancing
impulse (Ji-ping 2010b; Moser and Schnitzer 1985; Lazzarin 1995; Croba and
Kueny 1996; Lobanoff and Ross 2013). The material is spun and goes to the
impact plates. This crusher gives a much better control of product size because
there is less attrition. The impact crusher used at West Bokaro is completely
covered with plates, thus producing less dust (Srinivasan 2008). The fractured
pieces that pass through the clearances of the rotor and breaker plate enter a
second chamber created by another breaker plate (Croba and Kueny 1996;
Lobanoff and Ross 2013). Finally, material is transported to the third chamber
based on clearance. This grinding path is designed to reduce flakiness and gives
very good cubic particles.
• Process Overview
After the coal is mined it goes into pre-treatment (crushing), which is performed
in three stages: primary, secondary, and tertiary (Srinivasan 2008). Primary
crushing is done through roller crushers with a capacity of 750 tph and a
reduction ratio of 4; the feed size of 1000 mm is reduced to 250 mm after primary
crushing (Croba and Kueny 1996; Lobanoff and Ross 2013). The secondary
crushing is also done through the roller crusher with the same capacity of
750 tph and a reduction ratio of 3.3; here the size of the coal is reduced from
250 mm to 75 mm. Tertiary crushing is accomplished with an impact crusher
where coal size is reduced from 75 mm to 13 mm; this is a type of closed circuit
crushing. Finally, the optimal size of 13 mm is obtained, which coal is sent for
beneficiation (Gan et al. 1972; Yoshiie et al. 2012).
Beneficiation (Coarse Circuit)
In the mining industry, coal beneficiation or beneficiation in extractive metallurgy is

any process that improves (benefits) the economic value of the ore by removing the
gangue minerals, which results in a higher-grade product (concentrate) and a waste
stream (tailings) (Stepanoff 1948; Srinivasan 2008). Exemplary beneficiation pro-
cesses are froth floatation and gravity separation (Nadkarni and Williams 1983;
Yoshiie et al. 2012).
Equipment Used:
• Dense Media Cyclone (DMC)

The dense media cyclone provides a high centrifugal force and a low viscosity in
the medium, enabling much finer separations to be achieved (Feng 2006). Feed to
these devices is typically de-slimed at about 0.5 mm, to avoid contamination of
the medium with slimes and to minimize medium consumption (Fourie et al.
1980; Chen et al. 2012). The commonest form of DM cyclone is that made by the
Dutch State Mines in the 1940s. The DMC has an included cone angle of 20 . The
coal is suspended in the medium and introduced tangentially to the cyclone either
via a pump or by gravity feeding (Chen et al. 2012; Wood 1990) (Fig. 9).
• High-Frequency Screen
With high efficiency, small amplitude, and high frequency of screening, regarding
the working principle, the high-frequency screen differs from the conventional
screens. It creates good conditions for separating materials, especially small-sized
materials (Gan et al. 1972). When the machine operates, the low-frequency
electromagnetic vibrator vibrates the feeder. Then, the output part of the mesh
directly moves the whole screen (Ji-ping 2010a). At the same time, the high-
frequency electromagnetic vibrator shakes the middle of the mesh screen via a
rubber cushion (Ji-ping 2010a). The mesh screen is composed of three stainless
steel layers. The lowest layer, which is of high strength, is connected with the
Fig. 9 Cyclone installed at

coal plant
Fig. 10 Bird in standby

installed at Washery #2
shake motor; the other two layers are workable screens in mine processing (Croba
and Kueny 1996; Lobanoff and Ross 2013).
• Dewatering Material
In this machine from the term only signifies the removal of water and surface
moisture to enhance the quality of the product (clean coal) (Dzinomwa et al.
1997) (Fig. 10).
This section considers these two processes only, and other operations are
explained in the next sections. The entire apparatus is covered with a casing
called a “bowl” during the segmentation of coal.
• Process Review
Coarse circuit beneficiation provides the segmentation of coal by the gravity
separation method, which is then followed with other processes. Gravity separa-
tion uses a cyclone for segmenting coal in various forms: clean coal, middling,
and rejection (Srinivasan 2008; Gan et al. 1972). Screening is also done for
segmentation of coal by various methods followed by dewatering of coal using
the bird (Tao et al. 2000; Sabah et al. 2004).
Beneficiation (Fines Circuit)
The process of beneficiation has been discussed in the previous section with the
various characteristics.
Equipment used:
• Froth floatation
Froth floatation is a process for separating minerals from gangue by taking
advantage of differences in their hydrophobicity (Gan et al. 1972). Hydropho-
bicity differences between valuable minerals and waste gangue are increased
through the use of surfactants and wetting agents (Stepanoff 1948). Selective
separation of the minerals allows processing complex (that is, mixed) ores to be
economically feasible (Srinivasan 2008). The floatation process is used for the
separation of a large range of sulfides, carbonates, and oxides before further
refinement (Beamish and Blazak 2005). Phosphates and coal are also upgraded
(purified) by floatation technology. For froth floatation, the ground ore is mixed
with water to form a slurry with the desired mineral (Lazzarin 1995). It is then
rendered hydrophobic by the addition of a surfactant or collector chemical
(although some mineral surfaces are naturally hydrophobic, requiring little or
no addition of collector) (Stepanoff 1948). The particular chemical obtained from
the froth floatation cell depends on the nature of the mineral that is recovered from
the various processes (Moser and Schnitzer 1985; Lazzarin 1995).
This slurry (more properly called the pulp), a combination of hydrophobic and
hydrophilic particles, is then introduced to tanks known as floatation tanks or
floatation cells. These particles are then aerated to form air bubbles. The hydro-
phobic particles attach to the air bubbles, which rise to the surface, forming froth.
The froth is removed from the cell, producing a concentrate (“con”) of the target
mineral (Yoshiie et al. 2012). The minerals that do not float in the froth are
referred as “floatation tailings” or “floatation tails.” These tailings may be sub-
jected to further floatation stages to recover any valuable particles that did not
float the first time: this process is known as scavenging (De Korte 2010; Dwari
and Hanumantha Rao 2009). The final tailings after scavenging are usually
pumped for disposal as mine fill; they may also be pumped to tailings disposal
facilities for long-term storage.
• Thickener
A thickener is used to increase the concentration of a suspension by sedimenta-
tion, accompanied by the formation of a clear liquid (Osborne 1986). In most
cases, concentration of the suspension is high and hindered settling takes place .
Thickeners carry batches or continuous units, consisting of relatively shallow
tanks. The clear liquid is then taken off from the top and the thickened suspension
flows at the bottom (Yoshiie et al. 2012). The tank consists of one or more rotating
radial arms, from each of which are suspended a series of blades (Ji-ping 2010b),
shaped so as to move the settled solids toward the central outlet. In some cases
chemicals are also added in the thickener tank to make the solids settle faster, and
the rest flows from the bottom of the tank (Gan et al. 1972). A water sprayer may
be added at the top of the thickener tank to sink the froth on the top layer
(Nadkarni and Williams 1983). The direction of water spraying is similar to the
direction of the rakes so that the water spray does not counter the flow of water in
the tank. A high-rate thickener operates alternatively along with the thickener and
the other is kept on standby, or vice versa (Fig. 11).
• High-Rate Thickener
High-rate thickeners built as dedicated machines are available in sizes up to 40 m
in diameter, but retrofits of conventional thickeners are often larger in size (Gan
et al. 1972). When viewed from outside, high-rate thickeners look very much like
conventional machines except that their tanks have a greater height-to-diameter
ratio. Their height is derived from operation by calculating retention time and
reduced area. As to the internals, there are several approaches to the mechanism
of high-rate thickening. Design options include deep feed wells with progres-
sive flocculation along the incoming stream route (Ji-ping 2010b); another
is direct injection into the feed well or recirculation of liquid from the clear
zone to enhance settling rate by diluting the feed internally (Srinivasan 2008).
Fig. 11 Thickener installed

at beneficiation plant
There are also concepts that resemble a sludge-blanket that clarifies with feed
wells that are submerged in the sludge bed (Stepanoff 1948): these also
provide an additional benefit of trapping the fines to produce a clear effluent.
Unit number HRT is 101 (Fig. 12).
Parts associated with the high-rate thickener are as follows (Fig. 13):
1. Hydraulic power pack
2. Hydraulic cylinder
3. Hydraulic motor
4. Planetary gear box
• Vacuum Belt Filter
The belt filter (sometimes called a belt filter press) is an industrial machine used
for the solid–liquid separation process, particularly the dewatering of sludge in
the chemical industry, in mining, and in water treatment (Asmatulu et al. 2005).
The process of filtration is primarily obtained by passing a pair of filtering cloths
and belts through a system of rollers. The feed sludge to be dewatered is
introduced from a hopper between two filter cloths (supported by perforated
belts) that pass through a convoluted arrangement of rollers; water is squeezed
out of the sludge (Lazzarin 1995). When the belts pass through the final pair of
rollers in the process, the filter cloths are separated and the filter cake is then
Fig. 12 High-rate thickener

Fig. 13 Parts of thickener

scraped off into a suitable container (Lobanoff and Ross 2013). Belt filters use a
vacuum system to minimize off-gas and effluent during operations (Moser and
Schnitzer 1985).
• Reflux Classifier
This industrial machine separates fine particles on the basis of either density or
size, improving the efficiency of the process with its unique tilted design
(Honaker et al. 2000). A reflux classifier was developed by combining a conven-
tional fluidized bed with a system of inclined channels to achieve enhanced rates
of segregation of high-density particles and enhanced conveying of low-density
particles (Gan et al. 1972). The technique relies on the fact that the value of a
material is usually related directly to its density (Yoshiie et al. 2012). The device
consists of a system of inclined channels attached to a conventional fluidized bed.
The inclined channels permit significantly higher feed rates (Srinivasan 2008).
The reflux classifier can be applied to a relatively broad range of particle sizes and
can achieve higher recovery of valuable material than other water-based technol-
ogies (Wheelock and Markuszewski 1984). The technology has succeeded in
solving an existing processing problem by achieving the separation of coal
(Honaker 2010). It essentially helps in the recovery of premium, high-grade
metallurgical coal.
• Process Review
The fine flows from all the de-sliming screens are combined and sent to a froth
floatation (FF) tank, and then to a FF cell of capacity 100 tph via an FF pump: in
the FF cell the lighter coal particles leave as froth, are sent for dewatering to the
screen bowl centrifuge and vacuum belt filter (VBF), and then the final dried
clean coal is mixed with the coarse clean coal and stored in a clean coal
(CC) bunker (Ji-ping 2010b; Gan et al. 1972; Nadkarni and Williams 1983;
Yoshiie et al. 2012; Dzinomwa et al. 1997). Heavier gauge particles from FF
cells leave as tailings and are sent to the thickener; after thickening the underflow
is forwarded to a reflux classifier, and overflow from the reflux classifier goes to
the CC bunker while underflow is sent to a tailing dewatering plant (Duong et al.
2000).
Performance
The present chapter discusses the performance characteristics associated with

pumps and also helps in understanding relationships between the machine param-
eters and operations. The data in this chapter are taken from the operation of various
equipment during a particular process (Laskowski 2001). The graphs and charts
help in analyzing the characteristics of the equipment installed at the beneficiation
plant (Chen and Yang 2003; Dwari and Hanumantha Rao 2007). Such data are
crucial in analyzing the performance parameters of machines and also help in
enhancing the quality of the product as well as production efficiency (Lockhart
1984).
Site Details of Pumps
For a case study we used the TISCO plant. Coal handling is the major operation apart
from mining and other operations. Site details help in understanding the character-
istics of the pump installed at the washery plant.
Various parameters illustrated include model number, quantity, flow rate, slurry
head, particle size, specific gravity, pH value, temperature, application, sealing
arrangement, impeller mock, average working life, particle size, working hours,
pulleys, and motor. Table 1 also presents the specifications of all different pumps
installed at the plant, covering all the associated details.
Life Cycle of Warman Pump (Primary Pump)
Coal preparation is widely dependent on the operations associated with pumps, and
the pumps installed at the beneficiation plant are crucial. Key factors affecting the
life of a pump are given next.
Primary pump 172 also possesses various features related to the specifications.
The tables suggest improvements to be considered for enhancing pump working life.
Tables 2 and 3 present the detailed parameters of primary pumps 171 and
172, covering essential specifications including impeller, design capacity of each
pump, design head of the pump, motor rpm, pump rpm, media to be handled, specific
gravity of liquid, and motor efficiency (Mehta and Borio 1983). Details (in table)
highlighted by the yellow watermark in both sections of the pump show the required
rpm at which the pump should run, that is, 1040. A minor difference is observed
from both pumps in absorbed power consumption (BKW): in 171 it is slightly more
Table 1 Site details of pump
SL NO.-1 SL NO.-2 SL NO.-3 SL NO.-4 SL NO.-5 SL NO.-6 SL NO.-7

TAG NO:172/173 TAG NO:111/112 TAG NO:168/169 TAG NO:166/167 TAG NO:137/138 TAG NO:164/165 TAG NO:106/107/108
SITE DETAILS DESIGNED ACTUAL DESIGNED ACTUAL DESIGNED ACTUAL DESIGNED ACTUAL DESIGNED ACTUAL DESIGNED ACTUAL DESIGNED ACTUAL
MAKE WARMAN WARMAN WARMAN WARMAN WARMAN WARMAN WARMAN WARMAN WARMAN WARMAN WARMAN WARMAN WARMAN WARMAN
MODEL 10/8 RM 10/8 RM 10/8 RM 10/8 RM 8/6 RAH 8/6 RAH 8/6 RAH 8/6 RAH 10/8 RM 10/8 RM 6/4 DAH 6/4 DAH 8/6 EAH 8/6 EAH
QUANTITY 2 2 2 2 2 2 2 2 2 2 2 2 3 3
FLOW(m3/hr) 765 650 380 380 910 136 650
SLURRY HEAD(m) 58.1 44.9 65.3 65.3 28.5 52 41.8
PUMP RPM 898 923 923 555 1075 972
SP. GRAVITY 1.45 1.05 1.8 1.8 1.1 2 1.2
PARTICLE SIZE(mm) (-)275 MICR ( - )0.5 MM ( - ) 13 MM ( - ) 13 MM (-)0.5 MM (-250) MIRC (- )0.5 MM
PH VALUE 7 8.5 7 8.1 7 8.5 7 8.5 7 8.1 7 8 7 8
TEMPERATURE AMBIENT AMBIENT AMBIENT AMBIENT AMBIENT AMBIENT AMBIENT AMBIENT AMBIENT AMBIENT AMBIENT AMBIENT AMBIENT AMBIENT
PRIMARY PRIMARY SEC. SEC. SEC. SEC. OVER OVER
CYCLONE CYCLONE EFFLUENT EFFLUENT CYCLONE CYCLONE CYCLONE CYCLONE DILUTE DILUTE DENSE DENSE CLARIFIED CLARIFIED
APPLICATION FEED FEED PUMP PUMP FEED FEED FEED FEED PUMP PUMP PUMP PUMP PUMP PUMP
SEALING ARRANGEMENT EXPELLER EXPELLER EXPELLER EXPELLER EXPELLER EXPELLER EXPELLER EXPELLER EXPELLER EXPELLER EXPELLER EXPELLER EXPELLER EXPELLER
IMPELLER MOC A05 A05 A05 A05 A05 A05 A05 A05 A05 A05 A05 A05 A05 A05
MOTOR KW/HP 320 HP 220 HP 220/275 HP 220 HP 110 KW 100 HP 1480
MOTOR RPM 994 991 990 990 986 1465 1480
PUMP PULLEY SIZE 615X6 560X7 465X5 465X5 785X5 490X4 345X5
MOTOR PULLEY SIZE 560X6 515X7 440X5 440X5 500X5 340X4 510X5
TOTAL WORKING HOURS/DAY 22 22 22 22 22 22 22
RUNNING RUNNING RUNNING RUNNING
WITH WITH WITH WITH
PROPER PROPER PROPER PROPER
AVERAGE WORKING LIFE/PUMP 4200 LIFE 1400 1400 LIFE LIFE LIFE
Table 2 Primary pump 171

Washery II Primary pump
Description Unit Value
existing Ideal
Pump tag no. WS2/PMP/171/CLR
Make of pump Warman Warman
Model 10/8 RM 10/8 RM
Impeller F8147A05 F8147A05
Design capacity of each pump m3/h 765 765
Design head of the pump Mtr 58.1 58.1
Media to be handled Magnetite slurry Magnetite slurry
Specific gravity of liquid 1.4 1.4
Pump rpm rpm 992 1040
Efficiency at rated duty % – 63
Motor efficiency 90% 90%
Absorbed power consumption by the pump (BKW) KW 230 269
Amps drawn by motor at site amps 320
Motor KW/rpm/voltage 200/992/415
Note: This pump is running at lower than rated duty parameter
To obtain the flow of 765,000 m3/h @ 58.1 m, the head pump should run at rpm of 1040
Table 3 Primary Pump 172

Life cycle study of Warman pump at TISCO-West Bokaro
Washery II Primary pump
existing Ideal
Model 10/8 RM 10/8 RM
Amps drawn by motor at site Amps 255
Motor KW/rpm/voltage 200/992/415
Note: This pump it is running at lower than rated duty parameter
To obtain the flow of 765 m3/h @ 58.1 m, the head pump should run at the rpm of 1040
as compared to that of 172 in the existing case. Thus, current drawn from the motor
at site for 171 pumps is greater with respect to pump 172.
Graph of Head Versus Flow Rate for Two Distinct Pumps

(171 and 172)
The detailed study of both pumps has been mentioned in the section “Life Cycle of
Warman Pump (Primary Pump)” of this chapter covering all the associated factors
affecting pump working life. Figure 14 represents the relationship between head (m)
on the ordinate with respect to the flow rate (m3/h) on the abscissa for the primary
pump 171: this is the performance curve for horizontal Warman pump 10/8 m. The
arrow shown in Fig. 14 indicates the parameters at which the pump should operate
during segmentation.
The following information is shown below:
1. Flow: 765 m3/h

2. Head: 58.1 m
3. Speed: 1040 rpm
4. Efficiency: 63%
5. NPSHr: 6.1 m
Fig. 14 Head versus flow rate of 171

Details of pump 171 follow:
1. Pump
1.1. Discharge: 203 mm
1.2. Suction: 254 mm
2. Impeller
2.1. Vanes: 5
2.2. Vane phi: 549 mm
2.3. Type: closed
2.4. Metal: F8147
3. Frame rating (kw)
3.1. E: 120
3.2. EE: 225
3.3. F: 260
3.4. R: 300
3.5. FF: 425
3.6. FFX: 425
4. Minimum passage size: 65 mm
5. Seal: gland seal pump
6. Liner (normal maximum rpm)
6.1. Polymer: 920
6.2. Metal: 1100
The other graph gives details regarding primary pump. The graphs of primary
pumps 171 and 172 are similar because they have the same function during seg-
mentation. Figure 15 represents the relationship between head (m) on the ordinate
with respect to the flow rate (m3/h) on the abscissa for the primary pump 172. The
red arrow shown in Fig. 15 indicates the parameters at which the pump should
operate during segmentation. The following information is shown below:
1. Flow: 740 m3/h

1. Head: 32 m
2. Speed: 635 rpm
3. Efficiency: 69.4
4. NPSHr: 4.4 m
Details of pump 172:
1. Pump
2. Impeller
2.1. Vanes: 5
2.2. Vane phi: 686 mm.
2.3. Type: closed
2.4. Metal: G8147
2.5. Metal: FAM8147
Fig. 15 Head versus flow rate of pump 172

3.1. F: 260
3.2. FF: 425
3.3. FFX: 425
3.4. STX: 560
3.5. ST: 560
3.6. G: 600
3.7. GG: 900
3.8. T: 1200
6.1. Polymer: 715
6.2. Metal: 1100
The data represented here give us detailed information about the pumps installed
at the plant, and these data help us in understanding the difference between the two
pumps.
Life Cycle of a Warman Pump (Secondary Pump)
Coal preparation is widely dependent on the pump operation, and the pumps
installed at the beneficiation plant are crucial. Factors affecting the life of the
pump follow:
Table 4 Secondary pumps (167 and 168)

Life cycle study of Warman pump at TISCO – West Bokaro
Washery II Secondary pump
existing Ideal
Pump tag no. WS2/PMP/167/CLR and
WS2/PMP/168/CLR
Model 8/6 RAH 8/6 RAH
Absorbed power Consumption by the pump (BKW) KW 158 210
Amps drawn by motor at site amps 220 –
Motor KW/rpm/voltage 162/991/415 –
To obtain the flow of 380 m3/h @ 65.3 m the head pump should run at the rpm of 1176
Table 4 represents the detailed parameters of secondary pump of unit number

167 and 168, covering essential specifications such as impeller, design capacity of
each pump, design head of the pump, motor rpm, pump rpm, media to be handled,
specific gravity of liquid, and motor efficiency.
Graph of Head Versus Flow Rate for Secondary Pumps 167 and 168
Warman Pump (Secondary Pump)” of the given chapter, covering all the associated
factors affecting their working life. Figure 16 represents the relationship between
head (m) on the ordinate with respect to the flow rate (m3/h) on the abscissa for the
secondary pumps 167 and 168: this is the performance curve for horizontal Warman
pump 8/6AH. The red arrow shown in Fig. 16 indicates the parameters at which the
pump should operate during segmentation. The following information is represented
below:
1. Flow: 3 m3 80/h
2. Head: 65.3 m
3. Speed: 1176 rpm
4. Efficiency: 58%
Fig. 16 Head versus flow rate of secondary pump 167 and 168
Details of pumps 167 and 168:
1. Pump
2. Impeller
2.1. Vanes: 5
2.3. Type: closed
2.4. Metal: F6147
3.1. E: 120
3.2. EE: 225
3.3. F: 260
3.4. R: 300
3.5. FFX: 425
3.6. FF: 425
3.7. SX: 560
3.8. S: 560
6.1. Polymer: 715
6.2. Metal: 1500
The data represented here give us detailed information about the pumps installed
at the plant. These data help in understanding the differences between the two pumps
(Funk 1981).
Life Cycle of Warman Pump (Over-Dense Pump)
Coal preparation is widely dependent on the operations associated with this pump.
Parameters affecting the life of the over-dense pump follow:
Table 5 represents the detailed parameters of the secondary pump of unit number
165, covering essential specifications such as impeller, design capacity of each
pump, design head of the pump, motor rpm, pump rpm, media to be handled,
specific gravity of liquid, and motor efficiency.
Graph of Head Versus Flow Rate for Over-Dense Pump 165
Warman Pump (Over-Dense Pump)” of the given chapter covering all the factors
associated with them and affecting their working life. Figure 17 represents the
relationship between head (m) on the ordinate with respect to the flow rate (m3/h)
on the abscissa for the over-dense pump 165: this is the performance curve for the
Table 5 Over-dense pump 165

Life cycle study of Warman pump at TISCO – West Bokaro
Washery II Over-dense media pump
existing Ideal
Model 6/4 DAH 6/4 DAH
Impeller E4147A05 E4147A05
Design head of the pump Mtr 52 52
Media to be handled Coal+water Coal+water
Specific gravity of liquid 2 1.8
Amps drawn by motor at site Amps 84 –
Motor kw/rpm/voltage 75/1480/415 –
To obtain the flow of 136 m3/h @ 52 m, the head pump should run at rpm of 1463
Fig. 17 Head versus flow rate of over-dense pump 165
horizontal Warman pump 6/4AH. Arrow shown in Fig. 17 indicates the parameters
at which the pump should operate during segmentation. The following information is
represented here:
1. Flow: 136 m3/h
2. Head: 52 m
3. Speed: 1463 rpm
4. Efficiency: 53%
Other details of pump 165 are these:

1. Pump
2. Impeller
2.1. Vanes: 5
2.3. Type: closed
2.4. Metal: E4147
3.1 D: 60
3.2 DD: 110
3.3 E: 120
3.4 Q: 150
3.5 EE: 225
3.6 R: 300

6.1. Polymer: 1325
6.2. Metal: 1800
Curves of Other Horizontal Pumps
Detailed study of various pumps has been mentioned in the sections “Life Cycle of
Warman Pump (Primary Pump),” “Life Cycle of Warman Pump (Secondary Pump),”
and “Life Cycle of Warman Pump (Over Dense Pump)” of this chapter, covering all
the associated factors affecting their working life (Kubo et al. 1982). Figure 18
represents the relationship between head (m) on the ordinate with respect to the flow
rate (m3/h) on the abscissa for the pump 10/8AH. This curve represents the perfor-
mance curve for the horizontal Warman pump 10/8AH; it also provides information
regarding factors such as impeller and minimum passage size. The red arrow shown
in Fig. 18 indicates the parameters at which the pump should operate during
segmentation. The following information is represented below:
1. Flow: 740 m3/h

2. Head: 32 m
Fig. 18 Head versus flow rate for 10/8AH pump

3. Speed: 635 rpm

4. Efficiency: 69.4%
5. NPSHr: 4.4 m
Details of 10/8AH are these:
1. Pump
1.1 Discharge: 203 mm
1.2 Suction: 254 mm
2. Impeller
2.1. Vanes: 5
2.3. Type: closed
2.4. Metal: G8147
2.5. Metal: FAM8147
3.1 F: 260
3.2 FF: 425
3.3 FFX: 425
3.4 STX: 560
3.5 ST: 560
3.6 G: 600
3.7 GG: 900
3.8 T: 1200
6.1 Polymer: 715
6.2 Metal: 1100
Figure 19 represents the relationship between head (m) on the ordinate with
respect to the flow rate (m3/h) on the abscissa for the pump 10/8 M: this is the
performance curve for the horizontal Warman pump 10/8 M. The red line shown in
Fig. 19 indicates the parameters at which the pump should operate during segmen-
tation. Other details associated with pump 10/8 AM follow:
1. Pump
2. Impeller
2.1. Vanes: 4
2.3. Type: closed
2.4. MetA: F8145
3.1. E: 120
Fig. 19 Head versus flow rate for 10/8 M
3.2. EE: 225

3.3. F: 260
3.4. R:300
3.5. FF: 425
3.6. FFX: 425
6.1. Polymer: 920
6.2. Metal: 1100
respect to the flow rate (m3/h) on the abscissa for the pump 8/6AH: this is the
performance curve for the horizontal Warman pump 8/6AH. The red arrow shown in
Fig. 20 indicates the parameters at which the pump should operate during segmen-
tation. Other details for pump 10/8AH are as follows:
1. Pump
2. Impeller
2.1. Vanes: 5
Fig. 20 Head versus flow rate for 8/6AH
2.3. Type: closed

2.4. Metal: F6147
3.1. E: 120
3.2. EE: 225
3.3. F: 260
3.4. R: 300
3.5. FFX: 425
3.6. FF: 425
3.7. SX: 560
3.8. S: 560
6.1. Polymer: 940
6.2. Metal: 1500
respect to the flow rate (m3/h) on the abscissa for the pump 100SP: this is the
performance curve for the horizontal Warman pump 100SP. The red arrow shown in
Fig. 21 indicates the parameters at which the pump should operate during
segmentation.
Fig. 21 Head versus flow rate for 100SP pump
Details of pump 100SP are as follows:
1. Pump
1.2 Suction: 175 mm
2. Impeller
2.1 Vanes: 5
2.2 Vane phi: 370 mm
2.3 Type: closed
2.4 Metal: SP10206A
2.5 Metal: SP10206B
3.1 RV: 75
5.1 Unlined: 1400
Other Horizontal Pumps
Apart from primary pumps, various other pumps installed at the plant are essential in
the handling and preparation of coal (Burt 1999). In this section detailed information
is presented regarding other Warman horizontal pumps, including impeller, mini-
mum passage size, etc. Other details cover the factors affecting its working life.
Details for the 4-4 CXU pump are as follows:
1. Pump
1.2 Suction: 102 mm
2. Impeller
2.1 Vanes: 5
2.2 Vane phi: 306.07 mm
2.3 Type: closed
2.4 Metal: DXU41417
3.1 C: 30
3.2 CC: 55
3.3 D: 60
3.4 DD: 110
4. Minimum passage size: 39.37 mm
5. Seal: centrifugal sealed pump
6. Liner (normal maximum rpm): 2200
7. Curve revision: 1
The other details represented below are for a 3-3 cxu horizontal pump. The given
pump handles the various parameters associated with coal segmentation such as
impeller and minimum passage size. The details of the 3-3 CXU including all
parameters covering its working life are these:
1. Pump
1.2 Suction: 76 mm
2. Impeller
2.1 Vanes: 5
2.2 Vane phi: 220.22 mm
2.3 Type: closed
2.4 Metal: CXU3147
3.1 C: 30
4. Minimum passage size: 26.67 mm
5. Seal: centrifugal sealed pump
Issued May 5
The details represented next are for an 1.5-1AH horizontal pump. The given
pump also covers the various parameters associated with coal segmentation such as
impeller, minimum passage size, etc. Details covering factors affecting pump work-
ing life are provided in Table 6.
1. Pump
1.2. Suction: 38 mm
Table 6 Details of 1.5-1AH pump

Efficiency Updated
Revision Notes
Tests: 45 87B2 87B3 87B4
Reference
Issued Feb 1
2. Impeller
2.1. Vanes: 5
2.3. Type: closed
2.4. Metal: B1127
3.1. B: 15
5. Seal: gland sealed pump
Performance Curve
The primary selection tool is called a pump curve. Pump curves are essential data
about a given pump’s ability to produce flow against a certain head. When you are
reading a curve, the pump’s flow rate is on the top and bottom and its height for
pushing is on the sides.
According to the operation of the different pumps set up in the washery, these
performance curves show the relationship between head (m) on the ordinate with
respect to the flow rate (m3/h) on the abscissa for the pumps given here. These pumps
are represented below:
a. Pump HM250
b. Pump HH200
Figures 22 and 23 represent the performance curves of pump HM250 and pump
HH200, respectively. The curve is obtained on the basis of the operation performed
during the segmentation of coal.
Conclusion
This chapter gives us an ample amount of information about the working of pumps,
the characteristics of pumps installed at the plant, the performance characteristics of
these pumps, and the working operations associated with the segmentation of coal.
Fig. 22 Performance curve of pump HM250
The present chapter is broadly classified on the basis of these three parameters:
pump, process, and performance. The final segment of the chapter presents summa-
rized information regarding all three parameters associated in the preparation of coal,
represented as follows:
1. All pumps installed at the beneficiation plant are manufactured by Warman.

2. Pumps installed at the plant are indicated by a specific unique unit number.
3. The process runs under optimum conditions; thus, the firm is able to produce
1000 tons of coal per day from all three washery plants at TISCO, West Bokaro,
Jharkhand, India.
Fig. 23 Performance curve of pump HH200
4. A flow rate of 765 m3/h @ 58.1 m is obtained when the head pump runs at rpm
of 1040 for primary pumps 171 and 172.
5. A flow rate of 380 m3/h @ 65.3 m is obtained when the head pump runs at rpm
of 1176 for pumps 167 and 168.
6. Maximum efficiency obtained during the process is 69.4% for primary pump 172.
7. Minimum efficiency obtained during the process is 53% for secondary pump
165.
8. The average working time of a pump is 22 h/day.
9. Equipment associated with the process apart from pumps is manufactured by
Metso and other companies.
10. Performance parameters help in understanding the relationship between various

features associated with operations; that is, flow rate versus head graph for
several pumps in Section 4.0, etc.
11. All the data are taken during the operations performed by each of the machines.
12. The firm also takes care for the safety of the environment: thus, the organization
continues to plant trees at regular time intervals (70% of the area is under green
vegetation).
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Part II
Environmental Site Remediation
Technologies for Treatment of Colored
Wastewater from Different Industries 17
Shraddha Khamparia and Dipika Jaspal
Contents
Water Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 418
Sources of Colored Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
Characteristics of Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420
Harmful Effects of Colored Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420
Treatment Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
Physical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
Chemical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
Biological Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
Advanced Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
Comparison Between Different Treatment Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
Abstract
The delicate balance maintained by natural activities in the environment has been
drastically affected by several anthropogenic activities. Different industries con-
sume hazardous synthetic substrates and release their effluent, which leads to
contamination and deterioration of the natural resources in which they are expelled.
Human, as well as flora and fauna are greatly affected by these harmful substances
on exposure. Therefore identification and cleaning of the affected sites are of prime
importance in this arena. Numerous treatment methods have been employed for
S. Khamparia (*)
Symbiosis Centre for Research and Innovation, Symbiosis International (Deemed University),
Lavale, Pune, India
D. Jaspal
Symbiosis Institute of Technology, Symbiosis International (Deemed University), Lavale, Pune,
India
e-mail: dipikaj@sitpune.edu.in

https://doi.org/10.1007/978-3-319-73645-7_8
418 S. Khamparia and D. Jaspal
elimination of these toxic substances from nature. Moreover remediation technol-

ogies are based on the type of contaminant and its carrier. The chapter envelopes
numerous available technologies for treatment of wastewater generated from dif-
ferent industries employing dyes and pigments in their process. Several industrial
sectors such as textile, leather, paper, print, food, and cosmetics consume large
amount of coloring agents which are released into water system, thus degrading the
quality of the valuable resource. Description of the several treatment technologies
has been made at length encompassing their advantages and disadvantages.
The chapter is divided into subsections describing physical, chemical, biolog-
ical, and advanced methods. Further a comparative evaluation of available tech-
niques has been archived. Emphasis has been given on the latest techniques
taking sustainability and cost-effectiveness into account.
Keywords
Harmful effects · Water pollution · Physical methods · Chemical methods ·
Biological methods · Advanced methods
Abbreviations
AOP Advanced Oxidation Processes
BIS Bureau of Indian Standards
BOD Biological Oxygen Demand
COD Chemical Oxygen Demand
CPCB Central Pollution Control Boards
CWAO Catalytic Wet Air Oxidation
DO Dissolved Oxygen
NEA National Environment Agency
PAC Polyaluminum Chloride
PAFC Polyaluminum Ferric Chloride
PASiC Polyaluminum Silicate
WHO World Health Organization
Water Pollution
Earth is the only planet in which life is known to exist. Among various components
of life, water is the most important factor for sustenance of living beings. About
96.5% of water is in the seas, as saline water, which is not fit for domestic purpose;
3.5% is entrapped in glaciers, surface water, and groundwater; and only 0.07% is
potable water. The potable water is supposed to be the lowest fraction of available
water on the earth. However even being the most important factor for sustenance of
life, it is polluted in every possible manner by numerous anthropogenic activities.
Rapid industrialization, increased population, and increased living standards have
further intensified water pollution.
Accumulation of a broad range of organic substances by several textile, leather,
printing, paper, plastics, cosmetics, food, and pharmaceutical industries during their
processing techniques results in contaminated wastewater. Water bodies have been
17 Technologies for Treatment of Colored Wastewater from Different Industries 419
treated as the final receptors of a wide range of organic pollutants emerging from
various industries resulting in an increase in the concentration of toxic contaminant
in water. The presence of these contaminants proves to be detrimental as the toxic
chemicals present in the wastewater enter the aquatic system and damage the vital
organs of exposed organisms (Sponza 2003; Bianchi et al. 2011). Several genotoxic
and mutagenic effects on organisms have been alarming and a concern for various
researchers, environmentalists, and scientists working in this area. Therefore con-
servation and reclamation of this valuable resource are of utmost importance for the
survival of living beings. Although several regulating bodies and stringent rules have
been constituted to monitor the nature and quality of discharged effluents, most of
the industries do not fulfill those norms.
Sources of Colored Wastewater
Most of the substances used for daily purposes are impregnated with color. Different
kinds of dyes and pigment are used for the purpose. Color is commonly used in
clothing, furnishing, paper, printing, food products, and cosmetics. Textile, leather,
paper and printing, food, cosmetic, and pharmaceutical industries are primary
consumers of these dyes and pigments. These industries utilize large amount of
coloring agents, and a high percentage of these dyes and pigments are released from
these industries in the wastewater. Among all the industries, textile industries are
considered to be the prime consumers of dyes and pigment generating an enormous
amount of colored wastewater polluting the environment. Further paper and pulp
industry is known to consume large amount of dyes, biomass, energy, and materials
(Svensson and Berntsson 2014). Paper and pulp industries generate considerable
amount of wastewater with high possibility to affect the aquatic system adversely
either by production of slime, scum formation, formation of toxic by-products, or
presence of toxic color, ultimately resulting in loss of aesthetic value of the water
system (Pellegrin et al. 1999). Along with paper, pulp, and textiles, effluents from
tannery, leather, pharmaceutical, and cosmetic industries also pose a serious threat to
aquatic life. Sizing, scouring, mercerizing, dyeing, printing, and finishing are some
of the processes carried out in these industries. The effluent coming out from these
industries is mainly composed of unfixed dyes, salts, acids, alkali, auxiliaries,
cleansers, and other by-products. It is well documented that about 10–50% of the
unfixed dyes are present in the effluent (Khandegar and Saroha 2013) which is
released into the environment with or without primary treatment. The pollutants
present in these effluents are in much higher concentration with very low biode-
gradability (Di Iaconi et al. 2002). Several conventional, nonconventional, and
recently advanced oxidation methods have been employed for treatment of colored
effluents generated from these industries.
Currently emphasis has been laid in the search of greener, eco-friendly, and low-cost
wastewater treatment technologies (Szpyrkowicz et al. 2001; Sundarapandiyan et al.
2010; Krishnamoorthy et al. 2013). Some eco-friendly processes are adsorption using
natural materials, advanced methods, and biological methods involving environment-
friendly bacteria, microbes, plant extracts, and enzymes.
Characteristics of Wastewater
Wastewater coming out from textile, paper, printing, leather, food, and pharmaceu-
tical industries generally contains organic and inorganic chemicals, finishing agents,
surfactants, dyeing agents, dissolved solids, suspended solids, and total solids.
Table 1 gives a brief idea about the expected and actual ranges of various parameters
of wastewater generated from textile, paper and pulp, and tannery industries as per
several monitoring bodies such as World Health Organization (WHO), Central
Pollution Control Boards (CPCB), National Environment Agency (NEA), Bureau
of Indian Standards (BIS), etc. The composition of wastewater varies upon the
process adopted for the final product. Besides other chemicals and auxiliaries,
dyes share a major fraction of the colored effluent. Different kinds of dyes, such as
acidic, basic, vat, reactive, sulfur, metal-complex dyes, etc., are utilized by several
industries depending on the materials on which these need to be applied. More than
one million commercial dyes are known to be utilized by several industries with an
annual production of 70,000 tons (Robinson et al. 2001). Some of these dyes are
highly toxic, carcinogenic, and mutagenic to various aquatic species and humankind.
These are recalcitrant in nature due to which it becomes difficult to eliminate them
from wastewater. The chromophores (aromatic rings: anthraquinone, triphenylmeth-
ane, azo, etc.) and auxochromes (carbonyl, hydroxyl, amines, etc.) present in the
dyes are responsible for their complexity. Due to the vast structural diversity in
complex aromatic compounds present in dyes, along with high chemical, biological,
thermal, and photocatalytic stability toward degradation, dyes are thus inculpated as
the prime pollutants which need to be effectively removed from the water system.
Harmful Effects of Colored Wastewater
Expulsion of colored wastewater into the environment perturbs not only the physical
parameters but also the whole ecosystem. Parameters such as temperature, pH,
biological oxygen demand (BOD), chemical oxygen demand (COD), and dissolved
oxygen (DO) which are essential for the sustenance of aquatic life present in the
Table 1 Characteristics of wastewater generated from textiles, paper and pulp, and leather tanning
industries (Khandegar and Saroha 2013; Kamali and Khodaparast 2015)
Parameters of Textile Paper and pulp Leather BIS
wastewater industries industries industries standards
pH 8–12 4–13.5 Acidic 5.6–9.0
TDS (mg/L) 1500–30,000 – 37,000 2100
TSS (mg/L) 50–2000 40–7150 Low 100
BOD (mg/L) 50–3500 352–3000 Low 30
COD (mg/L) 250–20,000 1275–9065 27,600 250
Chlorides (mg/L) 100–700 – High 1000
Sulfates (mg/L) 50–350 – High 1000
Color Strong color Strong color Strong color Colorless
receiving water system are largely misbalanced by the addition of the effluents.
Predominantly, addition of even small amount of dyes disastrously affects the
intricate balance of aquatic system by decreasing the gas solubility, transparency,
and photosynthetic activity required for survival of aquatic flora and fauna. These
pollutants interfere with the essential oxygen transfer mechanism occurring at water-
air interface, leading to depletion of dissolved oxygen which is essential for healthy
aquatic life, and ultimately affect the self-purification system. Along with that,
severe impairment to human beings such as dysfunction of the central nervous
system, reproductive system, and vital organs like the kidney, liver, and brain has
been evidenced due to accumulation of dyes in a direct or indirect manner. In
addition, surface and groundwater contamination also occurs due to release of
these colored effluents into the nearby environment via leaching process. Produc-
tivity and delicate balance in the food chain are highly disturbed by the toxic
chemicals present in the wastewater (Auriol et al. 2006). Several mutagenic and
genetic ill effects have been seen on exposure to these carcinogenic colored sub-
stances (Leme and Marin-Morales 2008). Moreover, salts present along with dyes
lead to infertility of soil nearby and damage the aquatic life. Thus it becomes
important for these industries to treat wastewater.
In addition, on analyzing the need and current ratio of available water and
enormously increasing population, an urgent need eventuates to convert the waste-
water into some usable form such as irrigation fields for nonedible crops, reuse in
industries, fish production, and others (Molinos-Senante et al. 2011; Iqbal and Bhatti
2014; Manzoor et al. 2013). Safe disposal of effluents and their effective treatment
have thus recently become the global concern due to several harmful effects to the
environment and human health.
Treatment Technologies
Literature survey reveals several methods and techniques for eradication of color
from wastewater emerging from different industries, involving several physical
separation and chemical breakdown mechanisms and via biological degradation
using fungi, bacteria, and enzymes (Mondal 2008). In this section different treatment
technologies have been discussed which are employed for treatment of colored
effluents.
Physical Methods
Several physical methods such as filtration methods (ultrafiltration, nanofiltration,

reverse osmosis), coagulation method, and adsorption are utilized for effective
treatment of colored effluents.
Filtration techniques are widely used for treatment of colored effluents. Ultrafil-
tration, nanofiltration, and reverse osmosis have been utilized for reusing water and
chemical recovery also. However the filters used in these techniques largely depend
on the type of wastewater with variable size of pollutant and thus highly dependent
on the selection of filter to be applied (Porter 1997). Membrane filtration method is
proficient in eliminating all types of dyes. In addition, it requires less space for
equipment with almost zero generation of sludge. In this method treated water can be
completely recycled and can be used multiple times, thereby reducing the stress on
usage of freshwater. Further, drawbacks of the method lie in its large capital
investment for installation and membrane fouling problem with production of highly
concentrated dyebath which needs further treatment (Robinson et al. 2001). How-
ever membrane fouling problem can be solved by using coagulants and micro-
filtration pretreatment according to an experiment conducted by Vandevivere and
his coresearchers (1998). The dominant obstacle in this method lies in its costly
equipment and substrate-specific membranes and their disposals. Water obtained
after treatment can further be used in a subsidiary process of industries but not for
dyeing purpose as the water remains dirty and hard (Koltuniewicz and Drioli 2008).
Ultrafiltration usually acts as a pretreatment step followed by nanofiltration or
reverse osmosis to attain a high degree of purification (Barredo-Damas et al. 2010).
Nanofiltration technique operates at low pressure enabling low retention of mono-
valent impure ions, and thereby enhancing for option of reuse of brine solution
leading to high solute selectivity. It can even withstand at higher temperature and
hence can be employed for effluents having higher temperature (Scheafer et al. 2005;
Yu et al. 2012).
Reverse osmosis is known to be one of the effective methods since it assists in
eliminating both macromolecules and ions providing colorless treated water with
low salinity (Koltuniewicz and Drioli 2008). Besides these advantages, sometimes
extreme fouling problem takes place affecting the efficiency of membrane
performance.
Coagulation technique serves the purpose by coagulating the effluent by
establishing the electrostatic attraction between oppositely charged polymer mole-
cules and soluble dye molecules. Coagulants such as ferric salts, aluminum poly-
chloride, and polyelectrolyte are used often during the treatment process.
Coagulation and flocculation are widely used in treatment plants as a pre, post,
and main treatment in different countries. This method has been reported to be
effective for treating wastewater containing sulfur and disperse dyes (Marmagne and
Coste 1996). Here, the coagulant dosage is highly dependent upon the nature of
wastewater, dye concentration, and other processing steps. The drawback of the
method lies in the generation of excessive amount of sludge and total dissolved
solids in the treated water with high dependency of coagulants on pH of the water
system (Ates et al. 1997; Kabdasli et al. 1999). Other kinds of dyes such as cationic
dyes do not coagulate, while acidic, vat, reactive, and direct dyes coagulate but do
not settle. However to increase the removal efficiency for other dyes, large amount of
chemicals were required which may produce large volume of sludge.
Inorganic coagulants such as aluminum sulfate, ferrous sulfate, and ferric chloride
have been employed for treating tannery effluents and paper and pulp industries.
These assist in reducing the COD and suspended solids along with dye removal
capacity (Ates et al. 1997; Lofrano et al. 2006). A new variety of coagulants have
been introduced recently to improve the removal efficiency such as polyaluminum

chloride (PAC), polyaluminum silicate (PASiC), and polyaluminum ferric chloride
(PAFC) (Gao et al. 2005). Coagulation method followed by filtration and sedimen-
tation also has been employed for treatment of colored effluents. Electrocoagulation
has also been employed in paper and pulp industries since it was efficient in dealing
with pollutants having high molecular weight, dissolved solids, and organic matter.
Adsorption is a widely employed method for treating colored wastewater.
Adsorption being the most effective method of all not only removes the color but
also lowers the concentration of dissolved organic matter present in the wastewater.
Adsorption is the method dealing with the accumulation of substance at the solid
liquid interface when dealing with liquid wastes. Some of the factors on which the
technique depends are pH, temperature, contact time, particle size, and surface area
of adsorbent and dye-adsorbent interactions (Anjaneyulu et al. 2005). Earlier acti-
vated carbon was the most common adsorbent employed for effective removal of
different categories of dyes (Walker and Weatherley 1997). But utilization of
commercially activated carbon being an expensive affair has been replaced by
activated carbon derived from low-cost natural and waste materials recently. New
adsorbents have been studied and employed with an aim to achieve an eco-friendly
and cost-effective alternative.
Generally adsorbents are selected on the basis on dye-adsorbent affinity or
adsorption and regeneration capacity (Karcher et al. 2001). But here regeneration
of adsorbent is the major economic concern since procurement of adsorbent after
treatment is expensive. Zeolites, granulated ferric hydroxides, and polymer resins
were tested for their capacity, but the problem lied in their regeneration. Merit of the
method lies in the fact that it treats the effluents which are unaffected by conven-
tional biological treatment. It has proven to be an attractive alternative as it provides
variety of options for adoption of different types of adsorbents. This flexibility of
incorporating new materials for wastewater treatment, simplicity in design, and low
cost are some of the advantages which make it superior from all other methods.
Numerous natural materials like clay, fly ash, peat, agricultural solid wastes,
activated carbon derived from biomass solid waste, industrial by-products (hydrox-
ide sludge, fly ash, red mud, waste slurry, etc.), and inorganic oxides have been
widely tested for the removal of dyes from aqueous solutions (Robinson et al. 2002;
Ramakrishna and Viraraghavan 1997; Anjaneyulu et al. 2005).
Chemical Methods
Chemical methods largely involve the usage of several oxidizing agents such as
ozone, hydrogen peroxide, and permanganate for elimination of colored substances
from wastewater (Metcalf and Eddy 2003).
In the present scenario, electrocoagulation has fetched attention being a potential
technique for treating colored effluent because of its environmental compatibility
and versatile nature. The method involves the use of direct current source between
metal electrodes which are immersed in the effluent, causing dissolution of electrode
plates into the effluent. The metal ions at optimum pH lead to formation of metal
hydroxides and coagulated species that destabilizes the process and aggregate
particles or precipitates thus formed assist in adsorbing the soluble contaminants.
The process is considered to be a cost-effective one with minimal accumulation of
chemicals, thereby reducing secondary pollution and facilitating easy operation
(Zaroual et al. 2006). The drawbacks of application of this method lie in its inability
to treat effluents containing chlorides leading to generation of toxic by-products, and
hence the method can only be applied for effluents containing low dissolved solids
(Mollah et al. 2001).
Effluents having high concentration of salts, chlorides, and color can be effec-
tively treated by electrochemical oxidation (Szpyrkowicz et al. 2001;
Sundarapandiyan et al. 2010). The efficiency of the process is greatly affected by
the anodic materials used for treatment (Panizza and Cerisola 2004). Further,
electrochemical methods being more feasible and more economical have been
recently focused along with abovementioned methods. Wet oxidation process
using a two-metal catalyst was tested which exhibited higher efficacy than applying
a single-metal catalyst during treatment of wastewater (Garg et al. 2007; Herney-
ramirez et al. 2011). High color removal percentage with COD reduction was
obtained by using dual catalytic during the treatment. Other than above-explained
methods, chemical oxidizing agents have been used to remove the colored materials
from wastewater but with generation of toxic organohalides featuring its flaws.
Among all the oxidants studied, ozone with high reactivity is known to be the
most effective in eradicating the color from the wastewater (Alaton et al. 2002).
Hassan and Hawkyard directed toward the disadvantages of ozonation being inca-
pable of reducing color when disperse dyes and insoluble pollutants are present in
the wastewater (Hassan and Hawkyard 2002).
Biological Methods
Biological degradation of the colored effluent can be done either by anaerobic

process, by using microorganisms (fungal degradation, bacterial degradation,
enzymatic degradation), or by using yeasts. All these microbes are able to degrade
specific type of dyes, which becomes one of the limitations for applying the
biological process for treatment of wastewater. Moreover the methods require
large space and much time and are sensitive toward particular chemicals. Also
higher toxicity of most of the dyes is not easily degraded by this process (Hao
et al. 2000).
Fungal degradation is commonly seen in paper and pulp, tannery, and textile
industries (Yang et al. 2013). When compared to bacterial degradation, fungal
degradation can be well applied even to highly concentrated effluents (Singhal and
Thakur 2009; Singh and Thakur 2006). Fungi such as Phanerochaete chrysosporium
(Zhang et al. 2012), Trametes pubescens (Gonzalez et al. 2010), Basidiomycetous
(Malaviya and Rathore 2007), Pleurotus sajor-caju, and Rhizopus oryzae (Chandra
and Singh 2012) are widely used for removal of dyes from various industries.
Demerit of the process lies in its high-glucose requirement to speed up the metab-
olism of the microorganisms to increase the detention time.
It is known that dyes with aromatic compounds, nitro and sulfonic groups, are
recalcitrant to aerobic bacterial degradation (Claus et al. 2002). But few enzymes
such as azo reductases have the ability to break azo compounds producing aromatic
amines (Stolz 2001).
Enzymatic degradation involves the incorporation of oxygen under aerobic
conditions into the complex aromatic structure of pollutants leading to a breakdown
of the pollutant (Madigan et al. 2003).
Advanced Methods
To overcome the drawbacks of conventional methods such as low color removal

efficiency and low COD removals, advanced methods have been developed for
treating colored effluents. These methods are generally called advanced oxidation
processes (AOP) which include photocatalysis, photo-fenton, ozonation in combi-
nation with UV irradiation, hydrogen peroxide with UV irradiation, etc. AOP utilizes
strong oxidants such as ozone, hydrogen peroxide, and some metals in presence of
irradiation (Anjaneyulu et al. 2005). The mechanism involves the production and
utilization of free hydroxyl radicals in higher magnitude (Ince and Tezcanli 1999).
Fenton method (using H2O2) combined with ozonation as the prior step acceler-
ates the reaction, and the problem of sludge production is also tackled at the same
time. The method is relatively cheaper and effectively decolorizes the effluent with
high COD removals. H2O2 with UV irradiation is the most promising technology
used for treatment of hazardous colored pollutants recently, since it reduces the
sludge production to zero level, and high COD removals are also achieved by
adopting this method (Metcalf and Eddy 2003; Safarzadeh et al. 1997). It is worth
to be noted that maximum decolorization has been archived in literature when
treating effluent containing different kinds of dyes such as acidic, basic, reactive,
and direct dyes (Yang et al. 2005).
Moving forward, scientists have investigated the effect of some catalyst like TiO2 in
presence of UV irradiation which exhibited better results than others (Grzechulska and
Morawski 2002). Several combinations were tested which suggested that it was greatly
influenced by the nature of used dye, concentration of dye in effluent, and also pH of
the wastewater (Galindo et al. 2000). The serious drawback with AOPs is the formation
of toxic intermediates when organic pollutants were partially oxidized. Thus it is a
prerequisite to operate and monitor the whole process carefully, and toxicity tests need
to be done frequently to evaluate the status of the treated wastewater (Rizzo et al.
2009). Additionally these methods are expensive and encounter operational problems.
Catalytic wet air oxidation (CWAO) is another AOP which works at lower
temperature and pressure producing CO2 and H2O as the by-products and is applied
when the effluent contains low concentration of organic pollutants. AOPs are
considered to be the cost-effective process with advantages of sludge reduction,
COD reduction, high color removal percentage, odor removal, and effective
breakdown of micro pollutants. Effectiveness of the AOPs can be further enhanced

by adopting heterogeneous catalysts and solar energy and by combining biological
treatment methods.
Comparison Between Different Treatment Methods
Several treatment technologies have been investigated worldwide to mitigate the

problem of wastewater generated from various industries. Table 2 illustrates a
comparative evaluation of the various treatment processes employed for treatment
of colored effluents.
Table 2 Comparative chart between physical, chemical, biological, and advanced oxidation
processes employed for treatment of colored wastewater
Method Advantages Disadvantages
Physical methods
Membrane filtration Less space requirement High cost of membranes
No generation of sludge High cost of equipment
Treated water can be reused Lower productivity with time
Fouling of the membrane
Disposal problem
Coagulation Very effective for sulfur and Slow process
dispersive dyes Generation of large amount of
sludge
Large amounts of total dissolved
solids
Adsorption (using Decreases the organic content load Adsorbent regeneration is
activated carbon) expensive
Effective for variety of dyes Loss of adsorbent
Chemical methods
Electrocoagulation Economically feasible Large sludge production
Electrochemical Production of nonhazardous High electricity costs
reduction compounds as by-products
Ozonation No requirement of changing the Short half-life period
phase of ozone
No change in volume of effluent Low retention time
Biological methods Fungal degradation degrades dyes Time consuming
using enzymes
Decolorizes in 1 day Require large operational area
Effective in decolorizing azo and Ineffective for effluent
water-soluble dyes containing toxic elements
Effective only for specific dyes
Toxic by-products are formed by
anaerobic degradation
Advanced oxidation Sludge reduction High treatment cost
methods High color removal
Conclusion
The prime objective of all the treatment technologies lies in giving best results at
minimum costs. In this era of sustainability, there is an urgent requirement of
effective methods which not only treat wastewater but make it fit for domestic and
other purposes. Use of eco-friendly method involving a greener route, i.e., by
involving nature-based materials in the process, is the current requirement for an
overall efficient method. Environmentalists and the scientists working in this arena
are constantly investigating to improve the available technologies and to develop the
most appropriate treatment model for treatment of wastewater. The recent combina-
tion of methods and adoption of low-cost natural material opens a new perspective
for an effective, environment-friendly, and cost-effective technique. Although
several methods have been investigated, the current requirement of zero level of
impurity can only be attained by combining two or more methods. The selection of
an appropriate method for colored effluents solely depends on the characteristics of
effluent.
Cross-References
▶ Constructed Wetland: A Green Approach to Handle Wastewater

▶ Environmental Treatment Technologies: Adsorption
▶ Management of Hazardous Paper Mill Wastes for Sustainable Agriculture
▶ Techniques for Remediation of Paper and Pulp Mill Effluents: Processes and
Constraints
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Application of Novel Microbial Consortia
for Environmental Site Remediation and 18
Hazardous Waste Management Toward
Low- and High-Density Polyethylene and
Prioritizing the Cost-Effective, Eco-friendly,
and Sustainable Biotechnological
Intervention
Sinosh Skariyachan, Meghna Manjunath, Apoorva Shankar,

Nikhil Bachappanavar, and Amulya A. Patil
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
Conventional Methods of Plastic Waste Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 434
Landfills . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 434
Thermal Depolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 436
Merits and Demerits of Conventional Methods for Plastic Waste Management . . . . . . . . . . . . . . 437
Need for Novel Biotechnological Intervention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
Formulation of Novel Microbial Consortia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
Microbiology of Plastic-Degrading Bacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
Screening of Plastic-Degrading Microorganisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
Enrichment Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
Zone of Clearance Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
Microbiological Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
Morphological Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
Cultural Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
Biochemical Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
S. Skariyachan (*) · M. Manjunath · A. Shankar

R & D Centre, Department of Biotechnology Engineering, Dayananda Sagar Institutions,
Bengaluru, India
e-mail: sinosh-bt@dayanandasagar.edu
N. Bachappanavar · A. A. Patil
R & D Centre, Department of Biotechnology Engineering, Dayananda Sagar Institutions,
Bengaluru, India

https://doi.org/10.1007/978-3-319-73645-7_9
432 S. Skariyachan et al.
Molecular Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444

Amplified Ribosomal DNA Restriction Analysis (ARDRA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
Ribosomal Intergenic Spacer Analysis (RISA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Randomly Amplified Polymorphic DNA (RAPD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Environmental Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Biodegradation Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
Weight Loss Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
Gas Evolution Tests (Carbon Dioxide or Methane) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
Respiration Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
Plate Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
Enzyme Assays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
Soil Burial Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
Advanced Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
Mechanism of Degradation of Polyethylene by Microbial Consortia . . . . . . . . . . . . . . . . . . . . . . . . . . 449
Organisms Involved in Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
Mechanism of Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
Use of Surfactants for Enhanced Biodegradation of Polyethylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
Natural Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
Synthetic Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
Biofilm Formation During Plastic Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
Formation of Biofilm on Polyethylene Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
Analysis of Characteristics of Biofilm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
BATH Assay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 454
Biofilm Respiration Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 454
Factors Affecting Biofilm Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 454
Major Biodegradation End Products and Techniques Used for End-Product Analysis . . . . . . . 454
Fourier Transform Infrared Spectrophotometer (FTIR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
Gas Chromatography-Mass Spectrometry (GC-MS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
X-Ray Diffraction (XRD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
Atomic Force Microscopy (AFM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
Scanning Electron Microscopy (SEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
Infrared Methane Gas In Situ Analyzer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
Nuclear Magnetic Resonance (NMR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458
STURM Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458
Recent Advances in Scale-Up of Plastic-Degrading Microbial Consortia . . . . . . . . . . . . . . . . . . . . . 458
Anaerobic Digester . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
Scope of Enzyme Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
Scope of Bioinformatics and Computational Biology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
Biodegradation Databases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
Biodegradation Network-Molecular Biology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
University of Minnesota Biocatalysis/Biodegradation Database . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
MetaCyc and BioCyc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
Computational Biology Resources for Pathway Prediction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
PathPred . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
Biochemical Network Integrated Computational Explorer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
From Metabolite to Metabolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
Metabolic Tinker . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
MetaRouter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
Protein Structure Prediction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
Homology Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
Fold Recognition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
Ab Initio Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
Molecular Docking Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
18 Application of Novel Microbial Consortia for Environmental Site. . . 433
Molecular Dynamic Simulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469

Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
Abstract
Accumulation of plastics has been identified as one of the biggest threats to the
ecosystem due to the non-biodegradability and persistence of polyethylene for
extended period of time. Therefore, there is a high scope to manage the plastic
waste by eco-friendly, cost-effective, and novel biotechnological approach. The
current chapter focuses on the biodegradation of two forms of plastics, LDPE
(low-density polyethylene) and HDPE (high-density polyethylene), by means of
novel bacterial consortia screened from various sources. The chapter initially
focuses on conventional methodologies available for plastic waste management,
the merits and demerits of such technology, and need for novel biotechnological
intervention. The chapter later progresses with various approaches used for
formulating novel microbial consortia, the microbiology of important plastic-
degrading bacteria and their screening techniques, recent protocols used for
screening and characterization of plastic degradation bacteria, various techniques
used for the biodegradation studies, role of ideal environmental parameters for
effective degradation, mechanism of degradation of LDPE and HDPE by novel
microbial consortia, the role of biofilm formation on plastic degradation, major
biodegradation end products and approaches and techniques used for studying
these end products, and recent advances in the preservation and environmental
scale-up of novel plastic-degrading bacteria. The chapter finally illustrates the
scope of enzyme technology, bioinformatics and computational biology, molec-
ular modeling, and simulation aspects in biodegradation studies by novel micro-
bial consortia. The concepts highlighted in this chapter certainly provide new
dimensions and advancements in the field of environmental site remediation and
hazardous waste management.
Keywords
Environmental site remediation · Sustainable biotechnological intervention ·
Hazardous waste management · Novel microbial consortia · Plastic degradation
bacteria · Low-density polyethylene · High-density polyethylene
Introduction
The production of synthetic polymers (plastics) from petrochemicals is a major

advancement in the field of chemistry and in material sciences, which paved the
path for discovery of one of the most resourceful materials ever (Wei and
Zimmermann 2017). The applicability of plastics has intensified over the past few
years due to its combined features of strength, flexibility, lightweight, and easy and
low-cost production (North and Halden 2013). These properties have led to their
extensive use in artificial organs, engineered tissues, prosthetics, absorbable struc-

tures, medical delivery systems, and other medical applications (Saleem et al. 2015).
The major indelible component of municipal solid waste is plastic waste, comprising
plastic products primarily from low-density polyethylene (LDPE), high-density
polyethylene (HDPE), polypropylene (PP), and polyethylene terephthalate (PET)
(Miandad et al. 2016). The unique physicochemical property of polyethylene (PE) of
resistance to degradation leads to social and environmental hazard when such
products are discarded (Peixoto et al. 2017).
Around 311 million tons of plastic are produced in the world annually, nearly
26% of the plastics are recycled, 38% are discarded to landfill, and 36% are utilized
for energy recovery (Sharuddin et al. 2016; Wilkes and Aristilde 2017). The partly
degraded plastic debris of 5 mm diameter called microplastics have proven to pose
adverse effects by increasing organic pollutants on marine ecosystems (Van
Cauwenberghe et al. 2013). Due to high affinity to microplastics, these hydrophobic
complexes enter the food chains when consumed by marine wildlife (Law and
Thompson 2014). The accumulation of plastic wastes has shown to cause problems
such as premature birth, intrauterine growth retardation, preeclampsia, stillbirth,
cancer, and reduction in sex hormones in females. The efficient decomposition of
these plastic wastes takes about 1000 years (Kale et al. 2015). Hence, these non-
degradable plastics materials are considered as a major threat to the environment.
Plastics are usually dumped in landfills or are incinerated to eradicate them from
the environment. Both these practices cause very serious threats to the environment
and the ecosystem. The usual burning of plastics for its disposal produces some
noxious gases such as furans and dioxins. These dangerous greenhouse gases play an
important role in ozone layer depletion. Thus, there is growing concern for use of
efficient methods for biodegradation of nondegradable synthetic polymer without
harming the environment. Microorganisms are most effective in biodegradation of
plastics due to their ability to degrade most of the organic and inorganic materials
by utilizing plastic as the sole carbon source. One of the efficient strategies for
biodegradation of plastics is the enzymes produced by microorganisms; thereby
the rate of polymer degradation depends mostly on the mechanism of degradation
(Kale et al. 2015).
Conventional Methods of Plastic Waste Management
Landfills
The ultimate depository for heterogeneous mixture of plastics from residential,

industrial, and commercial source is the landfills. Landfills entail an enormous
amount of space and becomes very expensive due to the rising volume of municipal
waste plastics (MWP) being discarded. Additionally, landfills can discharge perilous
substances which cause an imbalance in the ecosystem (Wang et al. 2014). The
complexity and variability of plastic sources lead to the presence of composite
mixture of pharmaceuticals, personal care products, and other contaminants of
emerging concern (CECs) in landfill leachate (Masoner et al. 2014). The impact of
dumping plastic waste excessively in landfill has resulted in increasing attention due
to the presence of these contaminants in aquatic and terrestrial ecosystems. The
ubiquitous presence of CECs is regarded as a global phenomenon because of the
potential effects (toxicity, estrogenic activity, and carcinogenesis) caused on expo-
sure to very low concentrations (Masoner et al. 2016). The material and the energy
contained in plastics are lost completely in the process of disposing plastic in
landfills because it sequesters almost 100% of the carbon from the atmosphere.
Thus, discarding plastics in landfills is unsustainable and not an ideal strategy (North
and Halden 2013).
Thermal Depolymerization
Incineration
The process of controlled burning of waste at elevated temperatures around
900–1200 controlled residence time is termed as “incineration” (Ashworth et al.
2014; Li et al. 2015; Maya et al. 2016). In this conventional combustion process,
plastic waste is subjected to high temperatures resulting in the death of microorgan-
isms and a complete oxidation of organics due to which harmful gases are released
(Li et al. 2015). It has several benefits such as substantial decrease in the mass and
volume of the waste, prevention of disease transmission, and salvage of some
amount of energy used to produce these materials (North and Halden 2013). The
power plant required for incineration is smaller when compared to landfill, thus
taken into consideration by countries with restricted space for landfill (Li et al. 2015;
Nabavi-Pelesaraei et al. 2017). The by-products of incineration include fly and
bottom ashes, persistent organic compounds (dioxins and furans), solid waste
residues, and stack emissions such as acidic gases (carbon dioxide, carbon monox-
ide, oxides of sulfur, and nitrogen), heavy metals (cadmium, thallium, arsenic,
chromium, cobalt, copper, manganese, nickel, vanadium, and lead), and particulates
(Ashworth et al. 2014). The toxic components present in fly ash and the residues
exceed the admissible limits in concentration such as polychlorinated biphenyls
(PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dioxins
(PCDs), and polychlorinated dibenzofurans (PCDFs) which might cause mutagen-
esis, carcinogenesis, and teratogenesis (Wu et al. 2012). The partial combustion of
plastic and the unprecedented release of these by-products have caused environmen-
tal concerns (Saleem et al. 2015). In addition to environmental pollution, the
incineration of polyvinyl chloride (PVC) reduces the service life of the incinerator
by generating hazardous gases (HCl and dioxins) (Wang et al. 2014).
Pyrolysis
One of the alternative approaches for minimization of plastic waste and to reduce the
plastic disposal to the landfill is effective energy recovery. The plastics are acquired
from petrochemical source and, thus, can be converted to valuable energy having
high calorific value that can be reused to compensate the overall energy requirement
of the pyrolysis plant (Sharuddin et al. 2016). It is regarded as a tertiary recycling
technique and an advanced thermochemical treatment (TCT) method, a process
where thermal degradation of long-chain organic materials takes place with or
without the presence of catalyst called as catalytic pyrolysis and thermal pyrolysis,
respectively (Chen et al. 2014; Al-Salem et al. 2017). Pyrolysis occurs at varied
temperatures ranging from 300 to 900 C. However, the optimal temperatures for
plastic wastes were around 500–540 C in inert atmospheres (Chen et al. 2014). As it
requires an external source of energy (heat) for its development, it is considered as an
endothermic process. This process produces three major fractions of products: solid,
liquid, and gas. The solid fraction comprising majorly of ash and carbon (reliant on
the temperature employed), by its subsequent activation with CO2, steam, or both,
can be utilized for the manufacture of activated carbon or as fuel. The liquid portion
is composed of a combination of aliphatic and aromatic hydrocarbons. The gaseous
fraction consists of CO2, CH4, CO, H2, and other hydrocarbons (Maya et al. 2016).
By altering parameters such as reactant residence time and process temperature, the
process can be enhanced to increase the production of any of these elements (Lam
et al. 2016). The pyrolysis of HDPE resulted in the production of alkane gases was
studied by Conesa et al. (1994) using a fluidized bed reactor. It was observed that
thermal degradation of HDPE in a reactive extruder produced oily products with
future potential to refine fuels (Conesa et al. 1994; Saleem et al. 2015). Investiga-
tions depict that porous carbon performs significantly than commercially available
activated carbon; thus production of porous carbon is another application from
plastic waste. However, widespread application of plastic waste pyrolysis is limited
due to large volatilization owing to low yield, the burn-off effect under vacuum
condition, and its high-energy requirement during the process (Saleem et al. 2015).
Recycling
Recycling is an efficient approach to decipher the growing plastic waste generation

and the release of hazardous gases from the thermal treatment plants which has
increased those environmental apprehensions (Wang et al. 2014; Saleem et al. 2015).
Due to social, economic, and environmental reasons, it is receiving massive attention
for reducing the plastic waste (Wang et al. 2015). The varied chemical structure of
different types of plastics may lead to contamination of the key product leading to
low quality of the recycled plastics. Thus, polymers with different melting points or
thermal stabilities should not be mixed during the process of recycling (North and
Halden 2013; Wang et al. 2015). Plastic recycling encompasses four steps, namely,
collection, separation, processing/manufacturing, and marketing depending on trans-
parency, resin compound, and color (Ulrici et al. 2013; Wang et al. 2014; Sharuddin
et al. 2016).
The crucial step in recycling is the separation stage because of the presence of
various kinds of plastics in waste, with HDPE being the most common plastic and
currently the major recyclable material followed by LDPE and PP. Several tech-
niques are developed for separation of plastic such as gravity separation; electrostatic
separation, based on infrared analysis or laser scanning; and selective dissolution
(Wang et al. 2014). The techniques employed for the recycling of plastic material are
primary, secondary, tertiary, and quaternary recycling (Singh et al. 2016a). The
recycling of untainted disposed plastic without losing its properties into a new
product is primary recycling. This technique is also known as closed-loop recycling
since it is performed by the producer itself for postindustrial waste. In secondary
recycling, the molecular weight of the polymer drops due to chain scissions that
takes place in the occurrence of trace quantities of acids and water, resulting in the
reduction of mechanical properties (Ignatyev et al. 2014). Recycling of polymer
where the polymer chains are converted to smaller molecules via chemical processes
is tertiary or feedstock recycling. The characteristic conversion products are gases
and liquids that are employed for production of chemicals and fuels (Anke et al.
2012). Quaternary recycling is mainly used for processing of mixed and heavily
polluted wastes, involving recovery of heat, steam, and electricity through combus-
tion (Al-Salem et al. 2017). However, recycling of plastics is difficult as it could be
expensive due to the restraints on contamination of water and insufficient separation
before recycling (Sharuddin et al. 2016). Subsequent recycling depreciates the
strength of plastic component because of thermal degradation. Predominantly,
solvents having hydrogen-donor capability are involved in thermal degradation of
plastic affecting the hydrocarbon distribution and yield. Therefore, plastic waste is
discarded to landfills after the product loses its properties such as stability, durability,
etc. (Hamad et al. 2013; Sharuddin et al. 2016). The manufacturers prefer transparent
plastics since they can be easily dyed to form new products providing greater
flexibility. As a result, recycling plastic becomes challenging due to numerous
practical constraints to obtain high-value product (Sharuddin et al. 2016).
Merits and Demerits of Conventional Methods for Plastic Waste

Management
The oldest form of waste disposal is landfills; the plastic is buried under the ground
and monitored periodically. This mode of disposal is followed in most regions
because it is cost-effective than the other modes of waste disposal. Methane pro-
duced by these landfills by underground-decomposing materials can be captured for
further applications. These sites if monitored appropriately can later be reclaimed as
parks and farming sites. However, landfills have the potential to cause adverse
effects on the ecosystem. Landfills act as vectors causing infectious diseases if
monitored inappropriately (Masoner et al. 2014). Thus, plastic disposal in landfills
is an unsustainable method and will attenuate the usage of land for higher societal
value. The alternative method of waste disposal for plastics is incineration which
primarily reduces the need for land space for landfill. The incineration plant is
usually located near the waste generation sites, thus decreasing the cost and energy
associated with waste transportation (Nabavi-Pelesaraei et al. 2017). This method of
disposal leads to the discharge of noxious gases such as furans, dioxins, and
polycyclic aromatic hydrocarbons (PAHs). These plants are not user-friendly and
require expert to build, operate, and maintain.
To abate the problems caused by these two modes of disposal, recycling is
considered as the first line of defense in reducing the plastic waste. Recycling
reduces the energy and natural resources required for production of new plastics
(Singh et al. 2016a). Conversely, it has several obstacles, mainly, the sorting of
plastics, quality of the recycled plastic, and the present price of oil (North and Halden
2013). The recycled plastic can be a potent threat to the environment as it releases
volatile organic compounds (VOC). The high temperatures necessary for melting of
the plastic lead to carbon emission, thus contributing to the global warming. The
advancement in biodegradable plastics could be a reliable substitute to the synthetic
polymers, but not all the bioplastics obtained from renewable resources are biode-
gradable (Yates and Barlow 2013; Iwata 2015). However, novel approaches are
required to degrade the inert polymers present in the environment from a decade and
to alleviate the serious consequences posed by them (Peixoto et al. 2017).
Need for Novel Biotechnological Intervention
Polyethylene (PE) is an extremely hydrophobic long-chain polymer stabilized by

ethylene bonds. The two main plastics currently in high amounts in plastic waste
treatment and in use are low-density polyethylene (LDPE) and high-density poly-
ethylene (HDPE) (Wilkes and Aristilde 2017). The PE composed of branching
chains that are not tightly packed into a crystalline structure are categorized as
LDPE, while the ones with slight or no branching and the molecules forming
tough intermolecular forces by stacking are characterized as HDPE. The degradation
of these plastics is very slow in environmental conditions (Sangeetha et al. 2016b).
This is substantiated by the previous reports when PE sheet did not indicate
deterioration on incubating for 12 years, while partial degradation was observed
on burying the PE film for 32 years (Satlewal et al. 2008).
The main focus of research is biodegradation of plastics with microbial biotech-
nology methods which are more proficient for cleanup of these plastic wastes
compared to conventional approaches (Krueger et al. 2015; Skariyachan et al.
2016). The limitation for degradation can be overcome by potent microorganisms,
thus eliminating plastics from the polluted environment (Wilkes and Aristilde 2017).
The chemical degradation of a polymer carried out by the action of naturally
occurring microorganisms such as bacteria and fungi through enzymatic action
into metabolic products (e.g., CH4, H2O, CO2, etc.) is called biodegradation
(Mohan and Srivastava 2010). The products obtained on metabolism of plastics
are used to provide energy for vital carbon compounds, cellular machinery, and
secondary metabolites for further commercial applications (Peixoto et al. 2017). The
main cause for alterations in mechanical properties is by the cleavage of polymer
chains. The molar mass of the polymer depreciates by 50% even when a single endo
scission occurs in the polymer chain. These changes in the chemical structures lead
to great modifications in biodegradability. Embrittlement of the plastic material can

be observed when the plasticizers are removed by the action of microorganisms
(Mohan and Srivastava 2010).
Biodegradation is shown to occur in three stages: biodeterioration,
biofragmentation, and assimilation, without neglecting the involvement of the abi-
otic factors. The action of microorganisms (by chemical, enzymatic and mechanical
means) growing on the surface within a particular material results in biodeterioration
(Gu 2003). The microorganisms present in this method are distinct and correspond to
bacteria, protozoa, and fungi. The formation of consortia with a structured associa-
tion is called biofilm. The production of simple molecules is assisted by the
formation of varied microbial species in a definite order that upsurges the process
of biodeterioration (Lucas et al. 2008). Biofragmentation is a lytic phenomenon
required for the consequent event called assimilation. To obtain a combination of
oligomers and monomers, it is essential to cleave several bonds, and the energy to
complete scissions is of diverse origins: light, mechanical, biological, thermal, and
chemical. The microorganisms use different strategies to cleave the polymers either
by secreting specific enzymes or generating free radicals (Mateo et al. 2007).
Assimilation is the unique occurrence inside the microbial cells involving the fusion
of atoms from polymeric material fragments. This integration provides the microor-
ganisms with crucial sources of energy, electrons, and elements for the development
of cell structure. In this process, the microorganisms ingest the nutrient substrate
from the environment for their growth and reproduction (Lucas et al. 2008).
Advanced research needs to be carried out to understand the assimilation stage to
guarantee the real biodegradability of items. Polyethylene degradation is classified as
biotic and abiotic; the former is the degradation due to natural factors such as
temperature, UV irradiation, and pH, while the latter is deterioration caused by the
action of microorganisms that alter and consume the polymer resulting to changes in
its properties (Sen and Raut 2015). Around 65% of the earth’s biomass consists of
microorganisms, thus showing a probability of additional microorganisms proficient
in using PE as a carbon source. Reports have also shown the cumulative presence of
microorganisms associated with the process (Peixoto et al. 2017).
Formulation of Novel Microbial Consortia
The inadequacy of water solubility and the length of polymer molecules do not
enable the passage of polymers by microorganisms straight through their outer cell
membranes into the cells where utmost biochemical processes occur. The microor-
ganisms have developed a distinctive strategy to utilize polymers as a carbon and
energy source by releasing extracellular and intracellular enzymes. Extracellular
enzymes depolymerize these materials outside the cells. Polymers consist of differ-
ent blends (polymer) or low-molecular-weight additives (plasticizers) and are not
formed of only one chemical homogenous component, thus serving as a good
nutrient for the environmental microorganisms formed on the surfaces of the poly-
mer (Kyrikou and Briassoulis 2007). Growth in reaction rate is observed in the
presence of enzymes which have specific proteins with intricate three-dimensional

structures. It was observed that the reaction rate elevates to around 106–1020
without forming detrimental products (Mohan and Srivastava 2010).
The extensive application of plastics in our daily lives is mainly due to their light
weight, availability, and durability. Numerous environmental problems arise because
polymers are nondegradable; thus, there is a great need for biodegradation of plastic
wastes (Tribedi et al. 2012). Several reports revealed the occurrence of various soil
bacteria, actinomycetes, and fungi in the environment polluted with plastics gradually
tends to accustom to the acute surroundings and exploits these waste products as carbon
and nitrogen sources. Our previous study demonstrated that utilizing microorganisms
for degradation was highly sustainable and cost-effective (Skariyachan et al. 2015).
Two distinctive processes influence the action of microorganisms on polymer, i.e.,
direct and indirect actions. The former is the growth of microorganisms by using
degraded polyethylene as a nutritive component, while the latter is the effect of
metabolic substances produced by these microorganisms concerning discoloration or
additional degradation. The degradation of PE is determined by the growth of micro-
organisms, weight loss, carbon dioxide production, tensile strength, and changes in
percentage elongation during the process of degradation (Yamada-Onodera et al. 2001).
Our preceding studies suggested effective and eco-friendly degradation by novel
bacterial consortia because of significant benefits over the application of pure iso-
lates in xenobiotic degradation (Skariyachan et al. 2016). The action of consortia is
faster than single isolates due to their supportive activity (Anwar et al. 2013).
A group of microorganisms interlinked through relations, or groups of interspecific
semiosic links in biocoenosis, is called a consortium (Kull 2010). In order to
formulate a consortia of microorganisms that will work successfully, the bacterial
or fungal cultures have to be compatible. There should be no antagonistic effect
among themselves in order to degrade the polymer with high efficiency and perform
all metabolisms accurately. Antagonism is defined as an effect where one organism
inhibits another organism for its own benefit (Patowary et al. 2016).
Our recent study suggested that a consortia could be formulated based on the
biodegradation potential of individual isolates which was observed for a period of
120 days (Skariyachan et al. 2016). The microbial consortia have demonstrated that
a reduction in the mass of polymer is relative to an increase in the microbial
population. Further, there are cases that suggest a decrease in surface tension of
the cell-free medium indicating production of extracellular products (Roy et al.
2008).
The action of microorganisms upon polymer materials by utilizing them as sub-
strates for energy and biomass production occurs by different methods. The bio-
transformation of polymer compounds to nontoxic materials depends on the
presence and absence of carbon source. Co-metabolism and gratuitous degradation
are two distinct ways of microbial action on polymers. Co-metabolism is a form of
secondary substrate transformation wherein the enzymes produced for primary
substrate oxidation are proficient of degrading the secondary substrate, although
the secondary substrates cannot provide adequate energy to support the microbial
population. The phenomenon in which the polymer compounds are degraded by an
existing pathway and used as a source of energy for sustaining the growth of
microorganisms is called gratuitous degradation (Gupta and Kaushal 2015).
Bacteria can transform from a free-living regime to a surface-adapted multi-
cellular form called biofilm. The development of bacteria on surfaces is a stepwise
method including adhesion, growth, motility, and extracellular polysaccharide pro-
duction. Reports have revealed that these steps can be highly regulated by formu-
lating bacterial consortia than the individual isolates (Sivan et al. 2006). The
enriched colonization and microbial progression were indicated when consortia of
bacterial strains were employed for degradation of diverse polymers. The plasticizer
component of polymers can be degraded by Pseudomonas fluorescens FS1, Myco-
bacterium spp., and Coryneform spp. (Anwar et al. 2016). Lately, the biodegradation
of LDPE was examined in the incidence of two distinct consortia. The differential
action of inherently produced consortium-I and consortium-II of bacteria based on
primary nutritional screening was considered to preserve the environment as secure,
healthy, and dynamic. This method provides a broader approach toward biodegra-
dation of waste plastic which is creating environmental hazard (Anwar et al. 2013).
Fungi also promote the degradation of plastic by utilizing starch contained in the
polyethylene as the sole source of carbon. A study conducted to isolate microorgan-
isms from soil environment showed that growth of Penicillium simplicissimum YK
was enhanced on plates with 0.1% polyethylene while there was little or no growth
in plates without polyethylene. Thereby, the results provided a probability of the
fungi using polyethylene for their growth. It was also reported that the hyphae of the
fungus were more efficient for degradation of integral polyethylene than the spores.
The growth phase in pure fungal culture determines the time required for plastic
degradation. Since, the diminution in absorbance conforming to -C=C- showed that
some of the double bonds of PE were cleaved by Penicillium simplicissimum YK
(Yamada-Onodera et al. 2001).
A strain of Rhodococcus (C208) was isolated in a study using a two-step
enrichment procedure which was proficient in forming a biofilm on PE. The first
step was carried out in the soil along with PE, while the second one in a synthetic
medium which comprised PE as the sole carbon source. This actinomycete had the
potential to degrade up to 8% of the initial dry weight of soil-buried PE in around
4 weeks, and the addition of mineral oil to synthetic media for C208 enhanced the
degradation of polyethylene film by around 50% after 4 weeks of incubation (Mor
and Sivan 2008). These experimental studies show that further studies are required to
be performed to form novel microbial consortia for plastic degradation. The novel
consortia will aid in overcoming all the limitations that prevent the biodegradation of
plastic by microorganisms.
Microbiology of Plastic-Degrading Bacteria
Several types of microorganisms exist in the soil environment. The most important
in the study of plastic degradation is bacteria and fungi. Eubacteria and
archeabacteria are commonly found to degrade plastics in soil. They are further
classified as Gram-positive bacilli or cocci and Gram-negative bacilli or cocci.

However, Gram-negative cocci are rare and pathogenic prohibiting its utilization in
plastic degradation studies. Few common organisms found to degrade polymers in
the soil are Pseudomonas which is a Gram-negative, aerobic proteobacteria
consisting of numerous genera. Other organisms such as Rhodococcus ruber (aero-
bic, nonsporulating, nonmotile Gram-positive bacteria) and Brevibacillus
borstelensis (Gram-positive, aerobic, rod-shaped, endospore-forming bacterium) are
also known to degrade polymers by utilizing them as a source of carbon. Studies have
shown that fungal species such as Aspergillus niger and bacteria such as Pseudomo-
nas spp. or Vibrio spp. can exist in consortium exhibiting synergism (Muenmee et al.
2015). Bacteria that are known to degrade plastic in soil, compost, and sea water are
Flavobacterium spp., Staphylococcus spp., Micrococcus spp., Bacillus spp.,
Chelatococcus spp., and few thermophilic bacteria (Muenmee et al. 2016).
Screening of Plastic-Degrading Microorganisms
The screening is performed based on the type of sample used, and it involves
primary and secondary screening. For example, it can be sewage sample or soil
sample however; some of the standard approaches used for screening are listed
below.
Enrichment Technique
The enrichment process follows two steps in order to isolate the bacteria which can
degrade polymers. The initial enrichment is performed in the soil, and the next step is
carried out in liquid synthetic media. The soil samples from various landfills or
sampling sites containing polymers of various forms are collected. Soil samples and
synthetic media are added to test tubes along with the various forms of plastic. It is
incubated at 48 C for many weeks, and later the plastic sample is removed from the
tube. It is washed and dried, after which the plastic is weighed. The next step
involves the addition of polymer films, synthetic media along with soil sample
from which the polymer is isolated in a flask. The flask is incubated for a month,
and the plastic sample is weighed (Orr et al. 2004). In this method, the only source of
carbon is the plastic that is present. Hence, it requires some time for the organisms to
adjust to the environment and grow in order to degrade the plastic (Roy et al. 2008).
It is carried out in order to isolate the most efficient microorganisms in the process of
plastic degradation (Gajendiran et al. 2016).
Zone of Clearance Method
The zone of clearance method makes use of bacterial culture in minimal media.
The media consisting of polymer in the form of fine powder produce a zone of
clearance if degraded by the microorganism (Das and Kumar 2015). This zone can
be observed with the help of a stain known as coomassie brilliant blue. The
interaction between the dye and polymer aids to a fast and sensitive technique
for screening of microorganisms with polymer-degrading capability (Howard and
Hilliard 1999).
Microbiological Characterization
Morphological Characteristics
Gram staining is the technique which used to differentiate between two main types
of bacterial cells that are Gram-positive and Gram-negative. It is used for prelim-
inary analysis of unknown isolates (Beveridge 2001). The size is estimated by the
use of ocular micrometer where an eyepiece bearing a graduated scale is mounted
on the diaphragm along with a movable lens to visualize in the microscope
(Gonzalez-Ruiz and Bendall 1995). The motility test was performed by the hang-
ing drop technique which was employed on a glass slide with concavity (Titters
and Sancholzer 1936).
Cultural Characteristics
Nutrient media are a simple media which are generally used to provide all the
nutrients for the growth of organisms. It is composed of peptone, sodium chloride,
beef or yeast extract, and agar where the pH is maintained at 6.8–7.2 (Lapage et al.
1970). Nevertheless, minimal media are used to concentrate on a specific group of
organisms that can grow in the presence of minimum nutrients. The isolation and
screening of the bacteria with polymer-degrading ability are performed by using
modified minimal media. The media consist of fine plastic powder such as
low-density polyethylene, high-density polyethylene, and polypropylene devoid of
sodium citrate (Teeraphatpornchai et al. 2003). The sole carbon source is the plastic
powder along with other components such as dipotassium phosphate, potassium
phosphate, and magnesium sulfate. It is incubated for several days based on the
study being conducted and further enumerated in terms of CFU/g along with colony
characteristics (Skariyachan et al. 2016).
Further, selective and differential media are used to allow the growth of specific
type of organisms. MacConkey agar is differential and selective media for Gram-
negative organisms. The medium acquires its selective behavior due to the presence
of bile salts and crystal violet. Blood agar is an enriched media with the potential to
produce α-hemolysis, β-hemolysis, or γ-hemolysis (Buxton 2005). There are other
types of agar such as mannitol salt agar (MSA), eosin methylene blue (EMB) agar,
and other specialized media, and those are used based on the initial studies
conducted.
Biochemical Tests
The isolates are further subjected to standard biochemical tests such as:
Indole, methyl red, Voges-Proskauer, and citrate (IMViC) test to identify utilization
of tryptophan; formation of acidic, basic end products; and utilization of citrate
respectively (Lee et al. 2003)
Triple sugar iron (TSI) test to confirm results on fermentation of sugars (Hajna 1945)
Urease test for the detection of urease positive organisms (Midolo and Marshall
2000)
Catalase test to determine the breakdown of hydrogen peroxide (Taylor and
Achanzar 1972)
Nitrate test to detect the formation of nitrite and mannitol to conclude fermentation
of mannitol (Shittu et al. 2006)
Oxidase test to detect the production of cytochrome c oxidase (Jurtshuk and
McQuitty 1976)
Cellulose hydrolysis to detect cellulose-degrading organisms (Gupta et al. 2012)
Gelatin hydrolysis to find organisms that can liquefy gelatin (Whaley et al. 1982)
Molecular Characterization
16S rDNA Gene Sequencing

The utilization of polymerase chain reaction (PCR) and DNA sequencing in the
recent years has led to the usage of 16S rDNA sequencing which plays a fundamen-
tal role in identifying isolates of bacteria precisely. It is mainly useful in cases where
the bacteria possess an unusual phenotypic profile, the speed of growth is slow,
bacteria are unculturable, and bacteria are rarely occurring. One issue with the
method is its failure to automate (Patel et al. 2017). The sequences are further
studied for evolutionary relationships with the use of a tree constructed based on
neighbor-joining (NJ) method. It can later be visualized using several softwares such
as TreeView (Skariyachan et al. 2017). The 23S rRNA gene produces a better
phylogenetic tree as a result of larger variation in sequences when compared to
16S rRNA gene. Nonetheless, the use of this method is hindered due to lack of
existing wide-range microbial PCR amplification and primers to sequence (Gurtler
et al. 2014). In case of fungal species, 18S rDNA sequencing is performed.
Amplified Ribosomal DNA Restriction Analysis (ARDRA)
This protocol alternatively known as restriction fragment length polymorphism

(RFLP) involves the usage of rDNA amplified by polymerase chain reaction
(PCR) for restriction digestion. The community sample is initially amplified with
the help of PCR; after which, several restriction enzymes individually or in combi-
nations are used to cleave the DNA. The method works based on the differences in
rDNA sequences due to which a variation is created in restriction sites of enzymes.

On the use of a proper restriction enzyme, a unique fingerprint can be obtained for
particular strain or species.
The cleaved DNA is processed on a gel such as simple agarose or complex
polyacrylamide to obtain a pattern with varying size of fragments which is specific to
a community. One major limitation to this method is the lack of information to detect
a specific phylogenetic group belonging to a community (Sangeetha et al. 2016a).
Ribosomal Intergenic Spacer Analysis (RISA)
This technique is based on polymerase chain reaction (PCR) for the amplification of
intergenic region of prokaryotic ribosomes. The basis of the profile observed is
species-specific length polymorphisms. Change in the ribosomal intergenic spacer
(IGS) of rRNA operon rrl leads to the genetic fingerprint. The genetic region varies
in length due to enormous difference in sequence. This permits for taxonomic
identification of amplified samples based on conserved regions of operon rrl. The
chief advantage is that this technique can identify and differentiate different strains
and species that are closely related; whereas, methods such as 16S rDNA gene
sequencing do not succeed in doing so. However, only a fingerprint of the commu-
nity is obtained when this is implemented individually (Ciesielski et al. 2013).
Randomly Amplified Polymorphic DNA (RAPD)
This method does not depend on the sequence; however, it is dependent on poly-
merase chain reaction (PCR) which produces unique amplicons set for every genome
present so as to form a community profile of the sample. The primer used is only
around ten nucleotides in length leading to multiple attachments in a single target
DNA. The process of amplification takes place when two primers anneal in forward
and reverse directions near to each other to trigger a chain reaction. It is mainly
useful in identifying closely related species and also in characterizing a community.
This method does not provide any information regarding the composition of the
community (Babu et al. 2014).
Environmental Parameters
Several parameters such as pH, temperature, salinity, sunlight, humidity, stress,

water, culture conditions, and presence or absence of oxygen are involved in the
mechanism of degradation of polymers. They also play an important role on the
population of microbes along with its enzyme activity. In the case of fungi, lowest
pH induces maximum evolution of carbon dioxide gas and optimal activity. The
melting temperature (Tm) affects the enzyme activity to a great extent where they are
inversely proportional. Increase in enzymatic activity can be observed as the time is
increased. Molecular weight is one of the crucial parameters which favors degrada-
tion when at low ranges.
The high-order structures such as glass transition temperature, crystallinity,
crystal structure, and modulus of elasticity of polymers along with molecular weight
distribution are involved in the process of biodegradation (Tokiwa et al. 2009).
Substances such as stabilizers, additives, and antioxidants can possibly be toxic to
microorganisms leading to slower rate of polymer degradation (Kale et al. 2015). In
addition to this, the amount of amorphous and crystalline regions and breakable
bonds that are present such as ester or amide plays a main role. Branching or linearity
of the polymer also known as the structural complexity affects the rate of
degradation.
The form in which the polymer exists such as pellet, powder, film, or fibers affects
the rate of degradation and its efficiency (Arutchelvi et al. 2008). Our previous
studies suggested the role of high alkaline pH and temperature ran for the degrada-
tion of polymers (Skariyachan et al. 2017). One major problem is the time required
for the environmental degradation process as it may be very slow (van der Zee 2011).
The following are some factors that influence the biodegradation of the plastics
(Bhardwaj et al. 2013):
• Availability of functional group which increases the hydrophobicity

• Size, molecular weight, and density of the polymer
• Crystalline and amorphous regions available
• Structural complexity such as branching of the polymer backbone
• Presence or absence of easily breakable bonds
• Molecular composition
• Physical form of polymer
• Biosurfactants
Biodegradation Studies
Biodegradation is a process where polymers are degraded by natural activity either by

a simple process such as hydrolysis or a complex process. However, some polymers
are not degraded due to the complicated structure and other parameters. Temperature,
pH, chemical bond, etc. play an important role in such degradation mechanisms.
Some of the tests to measure degradation are described in the following section.
Weight Loss Method
In studies, the plastic is considered in the form of pellets and strips or any other
desired forms, and it is added into minimal media along with microbial culture of
interest. The weight is recorded at regular intervals for a required period of time. A
control consists of minimal media and polymer in the absence of microbial culture
(Skariyachan et al. 2015, 2016). To obtain the precise dry weight of the plastic film
or pellet, it is initially washed with 2% (v/v) sodium dodecyl sulfate (SDS) solution
and further cleaned with distilled water. The sample is further incubated overnight
and weighed. The following formula is used to calculate weight loss percentage
(Gajendiran et al. 2016)
Weight loss ð%Þ ¼ ðInitial weightFinal

Initial weight
weightÞ
100
Gas Evolution Tests (Carbon Dioxide or Methane)
In most cases, there is evolution of carbon dioxide or methane after the process of
polymer degradation by microorganisms. Hence, this is one of the main methods to
check for biodegradation. It consists of some well-known testing protocols such as
the laboratory-controlled composting test and Sturm test for aerobic conditions and,
also, anaerobic digestion test (ASTM 2011). These tests differ in the media compo-
sition, techniques, and inoculum used. These methods are used to directly measure
the mineralization and are easy to perform (van der Zee 2011). Sturm test is
performed by adding plastic strips into enriched media along with a control tube
(a tube containing no microbial culture). It is incubated for 4 weeks, and the CO2 is
measured gravimetrically. The gas evolved from biodegradation is collected in an
absorption flask with KOH and barium chloride, after which the precipitation of
barium chloride can be observed. The gas production is estimated by the CO2
evolved after the addition of barium chloride by comparing with the control
(Gajendiran et al. 2016). Since there is greater number of intermediate compounds,
mineral bed-based matrix was developed in recent years (van der Zee 2011).
Respiration Tests
The activity of microorganisms under aerobic conditions is determined by the usage

of oxygen. In the presence of oxygen, aerobic biodegradation takes place in order to
produce minerals such as CO2, H2O, SO2, P2O5, etc. Biological oxygen demand
(BOD) is the quantity of oxygen used up during the process of incubation and is one
of the parameters to evaluate the degree of biodegradation. It is usually expressed in
terms of percentage of theoretical oxygen demand (TOD) of the polymer. TOD is
defined as the amount of oxygen required for complete oxidization of substrate into
its mineral constituents. It is calculated with the help of composition of elements and
stoichiometry of oxidation or the measurement of chemical oxygen demand (COD)
(Bailes et al. 2013).
Plate Tests
This method is used to analyze the resistance of plastics to degradation caused by

microorganisms. It has now been improvised to test if a given polymeric material can
sustain the growth of organisms (ASTM 2009; Luckachan and Pillai 2011). The test
is based on placement of test material on mineral salts present in petri plates
without added carbon source. A standard mixture of inoculum-containing known
bacteria/fungi is sprayed on the plate and incubated for a fixed time period at a
constant temperature. The plate is then tested for growth and rate of growth (van der
Zee 2011).
Enzyme Assays
The buffered system consisting of many types of purified enzyme is mixed with a
polymer substrate. The kinetics of depolymerization or oligomer/monomer released
from the chain can be estimated under various conditions. It is a speedy process, and
quantitative information can be obtained (van der Zee 2011).
Soil Burial Method
This is one of the most common methods studied in biodegradation of plastics. It

involves the use of plastic in several forms with a particular measurement studied
under natural environmental conditions or under laboratory parameters. The initial
weight of the plastic is measured and buried in the soil at a desired depth. It is then
taken out after a specified period of time and washed with distilled water. After
which it is allowed to sit for 24 h to equilibrate with humidity and temperature. The
weight is measured, and studies have shown evident degradation of plastics
(Briassoulis et al. 2015).
Advanced Technology
Microorganisms have been identified as one of the best naturally occurring tools to
eliminate the toxic pollutants from the environment. Apart from the conventional
approaches, a new strategy called metagenomics is incorporated to screen and
identify a microorganism at genomic level. Metagenomics has found its application
in various soil and water environments. Recent studies have highlighted the ability
of metagenomic bacteria originating from the petroleum reservoirs (Dellagnezze
et al. 2014). The study focused on isolating both metagenomic clones and microbial
strains from petroleum reservoirs. It involved the study of single isolates or combi-
nations of isolates. The study revealed that metagenomic clones could degrade up to
94% of methyl phenanthrenes and phenanthrene (Dellagnezze et al. 2014). The
study can be extended to plastic-polluted environments to obtain higher percentage
of biodegradation.
Mechanism of Degradation of Polyethylene by Microbial

Consortia
Microorganisms can effectively be used in biodegradation due to their ability to

degrade most of the organic and inorganic materials using microbial enzymes and
hence is one of the most potent strategies. The rate of polymer degradation mostly
depends on the mechanism of degradation (Kale et al. 2015). Polyethylene degra-
dation by microorganisms using enzymes is a form of bioremediation. The success
depends on the biodegrading capability of native microorganisms or ones which are
exogenously applied (Patowary et al. 2016). The general mechanism involved in the
biodegradation of polyethylene by microbial flora is shown in Fig. 1.
Organisms Involved in Degradation
Microorganisms play an important role in plastic degradation. The microbial biodeg-

radation of plastics such as polyethylene has been accepted worldwide, and the process
is still underway for its enhanced efficiency (Kale et al. 2015). Different types of
microorganisms responsible for degradation of polyethylene are shown in Table 1.
Mechanism of Degradation
Various types of plastic such as polyethylene, polypropylene, polyvinyl chloride

(PVC), polycarbonate, polyethylene terephthalate, polypropylene, polystyrene, poly-
tetrafluoroethylene, and polyurethane are present in the environment as wastes (Begum
et al. 2015). Polyethylene degradation by microbial enzymes comprises mainly of two
steps: Firstly, the enzyme adheres to the polyethylene substrate and, secondly, the
enzyme catalyzes a hydrolytic cleavage (Bhardwaj et al. 2013; Wilkes and Aristilde
2017). Intracellular and extracellular enzymes in the microorganisms are responsible
for degradation of polyethylene. Microorganisms, with the help of extracellular
enzymes such as depolymerases and hydrolases, break down complex polymers
(polyethylene) into short chains of oligomers, dimers, and monomers which can then
pass through the bacterial membranes and act as a source of carbon and energy (Wilkes
and Aristilde 2017). This process is referred to as depolymerization. The end products
formed on degradation are mainly water and certain gases such as carbon dioxide and
methane (Bhardwaj et al. 2013). The overall mechanism is divided into four steps
(Ghosh et al. 2013):
• Attachment of the microorganisms to the surface of the plastic polymer

• Primary degradation of high-molecular-weight compounds of plastic polymer
• Growth of the organisms using the polymer as a sole source of carbon
• Ultimate degradation where lower-molecular-weight products are also used by
the microorganisms as source of carbon and energy
Fig. 1 General mechanism of biodegradation of polyethylene (LDPE) by microorganisms
Recent studies suggested that degradation occurs in two different ways: hydro-
biodegradation and oxo-biodegradation (da Luz et al. 2013; Wei and Zimmermann
2017). These processes occur due to the two different additives which are added
during manufacturing: starch and prooxidant. During hydro-biodegradation, methane
Table 1 Major microorganisms capable of biodegrading plastic polymers

Classification Major microorganisms References
Bacteria Acinetobacter baumannii, Arthrobacter spp., Arthrobacter Kale et al.
viscosus, Bacillus amyloliquefaciens, B. brevis, B. cereus, (2015)
B. pumilus, B. thuringiensis, Delftia acidovorans,
Flavobacterium spp., Micrococcus luteus, M. lylae,
Mycoplasma mycoides, Paenibacillus macerans, Pseudomonas
aeruginosa, Pseudomonas fluorescens, Rahnella aquatilis,
Ralstonia spp., Rhodococcus erythropolis, Staphylococcus
cohnii, Viscosus spp., Xylosus spp.
Fungi Aspergillus niger, A. ornatus, A. nidulans, A. cremeus, A. flavus,
A. candidus, A. glaucusi
Actinomycetes Amycolatopsis spp.
Table 2 Various enzymes responsible for biodegradation of plastic polymers

Source Enzyme Microorganism Reference
Bacteria Lipase Moraxella spp., Pseudomonas spp. Bhardwaj et al.
Esterase Enterobacter spp. (2013)
Serine hydrolase Pseudomonas stutzeri
Fungi Glucosidases Aspergillus flavus
Catalase, Aspergillus niger
protease
Urease Trichoderma spp.
Cutinase Aspergillus oryzae, Fusarium spp.
Lipase Rhizopus delemar, Penicillium spp.,
Rhizopus arrhizus
Serine hydrolase Pestalotiopsisi microspora
Manganese Phanerochaete chrysosporium
peroxidase
is emitted along with carbon dioxide. Addition of starch causes the formation of a
continuous starch layer making the polymer more hydrophilic and thus making it
accessible to degradation (Wei and Zimmermann 2017). During oxo-biodegradable,
the polymers are initially cleaved by nonenzymatic processes, such as photolysis and
chemical hydrolysis, and subsequently degraded by enzymes produced by bacteria,
fungi, or algae. These biodegradable polymers are further converted to carbon diox-
ide, methane, water, biomass, humus, and other substances (da Luz et al. 2013). Some
of the common enzymes produced during biodegradation are given in Table 2.
Use of Surfactants for Enhanced Biodegradation of Polyethylene
Surfactants are additives which help in enhancing the rate of biodegradation of

polyethylene and are generally classified into two types: natural and synthetic.
They help reduce critical micelle dilution (CMD) which is defined as concentration
of surfactants above which micelles form (Joshi et al. 2016) and surface tension
(ST) thus facilitating enhanced biodegradation of polyethylene.
Natural Surfactants
Natural surfactants or biosurfactants are surface-active amphipathic metabolites

produced by microorganisms during degradation of polyethylene (Patowary et al.
2016). Some of the biosurfactants are:
• Flagella
• Fimbriae
• Autotransporter proteins
• Curli
• Exopolysaccharide production
• Conjugative pili
Synthetic Surfactants
They can be added externally into the medium-containing polyethylene and bacterial
culture to enhance the rate of degradation. Tween 80, Tween 20, and CHAPSO are
some of the synthetic surfactants that promote the degradation of polyethylene (Wei
and Zimmermann 2017).
Biofilm Formation During Plastic Degradation
One of the key steps in the course of biodegradation is to identify biofilm-forming

microorganisms capable of degrading plastic polymers present as plastic waste
(Gilan and Sivan 2013). Owing to its potential risks such as persistence in nature,
antimicrobial resistance, and its role in the production of virulence factors, biofilm
formation by bacterial pathogens is studied extensively in medical fields. Biofilms
are communities of bacteria that exist within an extracellular polymeric substance
(EPS) which is composed of polysaccharides, proteins, and nucleic acids (Sanni
et al. 2015). Biofilms formed by a cluster of microorganisms allow cell-to-cell
interactions and ultimately lead to the establishment of complex, dense, and highly
structured biofilm populations encapsulated in a self-produced extracellular matrix.
The major events in the formation of biofilm by microbial consortia are shown in
Fig. 2. Biofilm formation on plastic polymers has been extensively studied using
scanning electron microscope (SEM) and atomic force microscope (AFM). SEM is
used to study the characteristics of the plastic surface after biodegradation by the
microbial consortia. AFM has been exploited to characterize microbial surface in
terms of structure of the polyethylene films post-degradation with higher resolution
three-dimensional images (Zhu et al. 2015).
Fig. 2 Major steps involved in the formation of biofilms include attachment of the bacteria onto the
surface, growth and proliferation, maturation, and detachment
Formation of Biofilm on Polyethylene Surface
The efficient biodegradation of polyethylene film depends on the formation of biofilm

as it enables the microorganism to effectively utilize polyethylene as a sole source of
carbon. The biofilm is reported to reach maturation wherein there is complete growth
of microorganisms and enhanced production of enzymes responsible for biodegra-
dation, after a period of 28 days (Yang et al. 2014, 2015b). Biofilm formation is
mainly divided into two steps, attachment and detachment (Petrova and Sauer 2016).
The process of biofilm formation in detail is as follows (Houdt and Michiels 2005).
• Initially there is a reversible attachment of the bacteria to the solid surface of

polyethylene. Bacteria approaches polyethylene by fluid stream or by motility.
The attachment occurs after they overcome the repulsive forces between the cell
and the surface.
• Transition from reversible to irreversible attachment of the bacteria occurs by
production of extracellular enzymes and/or by specific adhesions, i.e., pili or
fimbriae, which interact with the polyethylene surface to attach irreversibly.
• Early development of biofilm onto the plastic surface.
• Development of microcolonies in the mature biofilm. Extracellular polymeric
substances that serve as an adhesion matrix and trap nutrients are further devel-
oped. Pedestal-like structures, water channels, and pores are formed along with
the development of specific pattern for growth and different physiology and
metabolism by the bacteria to become mature biofilm.
• The mature biofilm breaks, and the cells are dispersed into the environment to
repeat the cycle. The cells return to the initial stage of reversible attachment to the
surface of polymer (Petrova and Sauer 2016).
Analysis of Characteristics of Biofilm
The characteristics of biofilm formed on the surface of polyethylene can be analyzed

using techniques such as: BATH assay and biofilm respiration measurements.
BATH Assay
The bacterial adhesion to hydrocarbon (BATH) assay is an assay which is used to

check the hydrophobicity of the bacterial biofilm. It is performed in nutrient
medium supplemented with phosphate urea magnesium sulfate (PUM) buffer
containing isolated bacteria or the consortia (Balasubramanian et al. 2010).
Biofilm Respiration Measurements
Using fluorescent redox probe 5-cyano-2, 3-ditolyl tetrazolium chloride (CTC),

the metabolic activity of the biofilm can be analyzed. It also helps in direct
monitoring of the respiration of the biofilm. The bacterial electron transport
system (ETS) converts the colorless nonfluorescent CTC to fluorescent insoluble
CTC formazan (CTCF), thereby representing the bacterial respiration depending
on the level of florescence. Usually, it is observed that the rate of respiration
increases gradually for a period of 1 month and later becomes constant (Mor and
Sivan 2008).
Factors Affecting Biofilm Formation
Bacterial biofilm formation can be influenced by the cellular surface hydrophobic-

ity of the polyethylene surface. It is observed that agents such as mineral oil and
Tween 80, capable of modulating hydrophobic interaction between polyethylene
and organism, influence both the bacterial adherence and the degradation of
polymer. Previous studies have demonstrated that the attachment of bacteria to
the surface of polyethylene can be enhanced by addition of mineral oil, whereas
Tween 80 interferes with biofilm formation (Tribedi and Sil 2013). Previous
studies suggested that increasing molecular rigidity improves resistance to bacte-
rial attachment. Molecular rigidity and the nonpolar side chains determine the
attachment of bacteria to the surface of polymers (Sanni et al. 2015). In case of PE,
bacterial attachment and formation of biofilm require alteration of cell surface by
oxidation reactions or the supplement of chemicals. Hydrophobic nature of bacte-
rial cell surfaces enhances their attachment to unmodified plastic polymers (Wilkes
and Aristilde 2017).
Major Biodegradation End Products and Techniques Used

for End-Product Analysis
On degradation of polyethylene by the microbial consortia, end products will be formed.

The major approaches used for the study of biodegradation are shown in Fig. 3. The
main approaches used for the study of biodegradation end products are explained below.
Assessment of plastic degradation
Mechanical Physical Chemical Degradation

properties properties properties end–products
DMTA SEM, AFM, FTIR, TLC, GC, GCMS,

XPS, DSC, NMR, EDS MALDI-TOF
XRD, TGA
Fig. 3 The major approaches used for the characterization of the end products of biodegradation by
microbial consortia. DMTA, dynamic mechanical thermal analysis; SEM, scanning electron micros-
copy; AFM, atomic force microscopy; XPS, X-ray photoelectron spectroscopy; DSC, differential
scanning calorimetry; XRD, X-ray powder diffraction; TGA, thermogravimetric analysis; FTIR,
Fourier-transform infrared spectroscopy; NMR, nuclear magnetic resonance; EDS, energy-dispersive
spectroscopy; TLC, thin-layer chromatography; GC, gas chromatography; GC-MS, gas
chromatography-mass spectroscopy; MALDI-TOF, matrix-assisted laser desorption/ionization-time
of flight
Fourier Transform Infrared Spectrophotometer (FTIR)
The analysis includes passing infrared (IR) radiation through polyethylene and
depends on the percentage of radiation transmitted by polyethylene incubated with
bacterial cultures. The resulting spectrum comprises peaks for molecular absorption
and transmission of the sample (Divyalakshmi and Subhashini 2016; Chakraborty
and Das 2017). FTIR analysis is carried to check the carbonyl index (CI). The
carbonyl index is a measure of concentration of carbonyl groups such as acids,
aldehydes, and ketones. It can be calculated as follows (Pramila and Ramesh 2015):
1
Carbonyl Index ðCIÞ ¼ Absorbance at 1715 cm
Absorbance at 1465 cm1
Major groups are broken down and/or formed due to the activity of microorgan-
isms on polyethylene surface. Previous studies suggested that peak at 4000 cm1
represents the formation of >C=O group; at 1000 cm1 represents C–Cl bonds; at
2750–3000 cm1 represents changes in alkane group (C–H) (Divyalakshmi and
Subhashini 2016); at 1710–1750 cm1 represents formation of ketone or aldehyde
C=O groups; at 1000 and 1700 cm1 represent oxidized fractions, such as moieties
containing –OH groups (Esmaeili et al. 2013); and at 1465 cm1 represents CH2.
Gas Chromatography-Mass Spectrometry (GC-MS)
This technique provides useful information about the molecular structure of the
macromolecules. It also helps to study the gaseous products produced during
degradation of plastic polymer. In recent years, the method is used in the structure
study of the biodegradable synthetic polymer, comprising the following (Chakraborty
and Das 2017):
• Verification of chemical homogeneity of the polymer and to determine the

chemical structure of end groups
• Determination of the molar mass and weight distribution of degradation end
products
• Determination of the chemical composition and distribution of the sequence of
units to individual macromolecules of copolymers
One of the previous studies suggested the presence of compounds such as

2-butene, 2-methyl, acetone, ethane, alkanes, aromatic compounds, and fatty acids
such as hexadecanoic acid and octanoic acid based on GC-MS analysis (Pramila and
Ramesh 2015).
X-Ray Diffraction (XRD)
The level of crystallinity of the plastic can be assessed using this technique. As the
biodegradation progresses, the crystallinity of plastic is seen to decrease due to
the breakage of bonds by the microbial consortia. Previous studies carried out
with pretreatment of polyethylene with UV radiation have shown that the peaks
of UV-irradiated films are higher than that of non-UV irradiated. This
difference illustrates that oxidation of the plastic increases its crystallinity (Esmaeili
et al. 2013).
Atomic Force Microscopy (AFM)
AFM helps to analyze the surface morphology of the polyethylene films, degraded
by the action of microbial consortia. AFM observations are based on interatomic
forces. The plastic becomes rough due to the formation of cracks and grooves on the
surface post degradation (Ojha et al. 2017; Chakraborty and Das 2017).
Scanning Electron Microscopy (SEM)
SEM is an instrument employed to check the biofilm formation and to confirm

degradation. The biodegradation of low-density polyethylene by microbial consortia
is shown in Fig. 4. Dehydrated polyethylene is sputter-coated with a gold layer. The
sputtering can be achieved after passing the pure and dry argon gas in the coating
chamber, under vacuum. The plate voltage was 2000 V, and the current passed was
15 mA. A thickness of 2 nm of gold was achieved during a sputtering time of 10 s.
The polyethylene was then examined under the scanning electron microscope. Few
a b
100 μm EHT = 5.00 kV Signal A = InLens 2 μm EHT = 5.00 kV Signal A = InLens

WD = 9.5 mm Mag = 231 X WD = 9.3 mm Mag = 12.42 K X
c
2 μm EHT = 5.00 kV Signal A = SE2

WD = 9.3 mm Mag = 19.08 K X
Fig. 4 The biodegradation of low-density polyethylene by formulated microbial consortia charac-

terized by scanning electron microscope: (a) control, (b) attachment of rod-shaped bacterial
consortia on the surface of low-density polyethylene, (c) structural changes in LDPE observed
during the biodegradation by microbial consortia
structural changes such as grooves, cracks, damaged layer, fragileness, pits, and
roughening of the surface can be observed along with the biofilm formed (Ojha et al.
2017). Using BacLight Bacterial Viability Kit along with SEM helps determine the
cell viability. The kit helps in monitoring the viability of bacterial populations as a
function of the membrane integrity of the cell. The live cells take up the green dye
and hence appear green in the SEM image, whereas the dead cells take up red dye
and appear red (Sivan et al. 2006).
Infrared Methane Gas In Situ Analyzer
It is an instrument employed to analyze the methane gas produced along with biogas.
Usually, it is seen that as the days of incubation increase, the methane produced also
increases (Wan et al. 2013).
Nuclear Magnetic Resonance (NMR)
Nuclear magnetic resonance (NMR) is the technique of determining physical and

chemical properties of atom and molecules by exploiting their magnetic properties.
It helps to study the detailed structural information, dynamics, reaction rate, and
the chemical environment of molecules by exploiting the phenomenon of NMR.
Molecules having nuclei possessing spin can be investigated by this technique;
therefore, organic molecules are the primary compounds for analysis. The resonant
frequency, the energy of the absorption, and the intensity of the signal is dictated
by the strength of the magnetic field. NMR response of free induction decay is
generated by exciting the sample with radio-frequency pulse. Thus, two spin states
are generated in the presence of external magnetic field wherein one aligns with the
magnetic field and the other aligns opposite to the field. This produces a difference
in energy between the two spin states, thus increasing the field strength. Thus, it
gives the chemical shift which is the resonant frequency of a nucleus relative to a
standard in a magnetic field and determines the structure of the molecule
(Chakraborty and Das 2017).
NMR results are obtained in the form of a graph with peaks at different ppm. In
one of our previous studies involving 1H-NMR analysis of LDPE and HDPE sample,
it was observed that additional triplet peak between 1.0 and 1.5 ppm and a peak
between 3.5 and 4.0 ppm specify the degradation of plastic, followed by the
formation of a methyl group and an aldehyde moiety as end products post degrada-
tion (Skariyachan et al. 2017).
STURM Test
Carbon dioxide evolved as a result of polymer degradation can be studied using

this test. All degradation types produce carbon dioxide. The gas evolved is
trapped using Durham’s tube and is measured using Steinfurth CO2 tester which
is further compared with the standard. Previous studies have shown that all types
of biodegradation by microorganisms have proven to produce carbon dioxide
(Shah et al. 2013).
Recent Advances in Scale-Up of Plastic-Degrading Microbial

Consortia
The experiments carried out until date are all in small scale, and hence, for escalation
to mid-scale or larger scale, techniques such as anaerobic digester and soil burial
method are employed. The process can also be carried out in a reactor.
Anaerobic Digester
Plastic wastes are added to the digester in small scale along with the bacterial culture.
The culture is retrieved. The content of carbon dioxide, methane, and biogas
produced is then retrieved and used as a source of fuel. The study at mid-scale is
carried out for 5–10 years. The rate of biogas produced increases at the initial part of
the experiment and then comes to a steady state (Wan et al. 2013).
Scope of Enzyme Technology
Enzyme-mediated processes have rapidly gained importance in detoxification of

municipal solid waste, waste water, hazardous waste, and polluted soils (Le-Roes-
Hill and Prins 2016; Shah 2017). Among biological approaches, microbial enzymes
are highly efficient for the biodegradation of plastics due to their stability, target-
specific catalytic activity, and ease of production than plant and animal enzymes
(Choi et al. 2015; Singh et al. 2016b). These enzymes are specific in their action on
substrates; hence, multienzymatic processes can be designed to specifically target
selected forms of plastic such as low- and high-density polyethylene that are
detrimental to the environment (Brodhagen et al. 2015). The use of microbial
consortia for environmental site remediation and hazardous waste management is
extensive with a large number of enzymes participating in the biodegradation of
toxic pollutants (Shah 2017). The process of bioremediation mainly depends on the
enzymatic activity of microorganisms (Dash et al. 2013). The combination of
microbial enzymes has been employed for the bioremediation of hazardous wastes
containing toxic chemical compounds such as aromatic amines, nitriles, and phenols
either by degradation or bioconversion to nontoxic products (H2O, CO2 or CH4)
(Nikolaivits et al. 2017). Furthermore, with the recent biotechnological advances in
the field of protein and genetic engineering, microorganisms can be genetically
modified and cultured in large quantities for the production of enzymes at low cost
to meet increasing demands (Dash et al. 2013).
Only certain species of bacteria and fungi have proven their ability as potent
bioremediation agents (Brodhagen et al. 2015; Paco et al. 2017). The process of
microbial degradation depends on the type of plastic, the organisms, and the
environment involved (Rayu et al. 2012). However, there will always be the
involvement of extracellular and intracellular enzymes which help in the degradation
of polymers at one stage or another in the process (Karigar and Rao 2011). Biodeg-
radation of plastics is primarily due to the action of enzymes (hydrolysis and
oxidation) that lead to the cleavage of the long-chain polymers into oligomers and
monomers (Brodhagen et al. 2015). Microorganisms can survive in extreme envi-
ronments, yet most of them prefer optimal conditions which are difficult to achieve
outside the laboratory (Dash et al. 2013). The major limitations of bacterial growth
which is under the influence of temperature, pH, moisture content, oxygen, the
bioavailability of nutrients, contaminants, and the presence of other toxic com-
pounds can be addressed by the immobilization of enzymes (Khan et al. 2013).
Similarly, the gene expression of enzymes in microbial cells is regulated by specific
inducers, repressors, and cofactors which may often be absent at the site of biore-
mediation (Quecholac-Pina et al. 2016). Hence, to overcome these drawbacks,
investigations have been focused on developing methods to stabilize and utilize
enzymes preferably by immobilization onto solid supports. Further, immobilized
enzymes are not inhibited by the inhibitors of microbial metabolism. They can be
used effectively at both low and high pollutant concentrations under extreme
conditions. Immobilized enzymes specifically act against a given substrate, while
microorganisms may prefer more easily degradable compounds than the pollutant
(Rayu et al. 2012). In addition to being more mobile than microorganisms because of
their smaller size, these features render enzymatic techniques, eco-friendly pro-
cesses, and enzymes as biocatalysts (Rao et al. 2010; Choi et al. 2015). Additionally,
the enzyme that has demonstrated potential degradation of a polymer in vitro does
not guarantee similar in situ activity. There will be substantial variation during scale-
up as a laboratory in vitro assay performed under optimized conditions does not
completely represent the natural environment (Rao et al. 2010). Furthermore, if the
native substrate for the microbial enzyme(s) is present in the environment, it may
outcompete the plastic for enzyme binding (Quecholac-Pina et al. 2016). The
degradation of foreign compounds in the environment is often performed by micro-
bial consortia where a single species might initiate the process but may not be able to
complete it independently (Khan et al. 2013; Shah 2017). Hence, development of
techniques for the immobilization of multienzymes along with cofactor regeneration
and retention systems is yet to be explored in the design of complex biochemical
processes involving a series of chemical conversions.
Immobilization methods can be divided into two general classes, namely, chem-
ical and physical methods. Physical methods are usually characterized by weaker
interactions such as hydrophobic interactions, van der Waals forces, hydrogen
bonds, ionic binding and affinity binding of the enzyme with the support material,
or mechanical containment of enzyme within the support (Es et al. 2015). In the
chemical methods, the formation of covalent bonds is achieved either through
thioether, ether, carbamate, or amide bonds between the enzyme and support mate-
rial involved (Eibes et al. 2015). There are four principal techniques for immobili-
zation of enzymes (Homaei et al. 2013), namely, adsorption, entrapment, cross-
linking, and covalent bonding (Fig. 5).
Physical adsorption can be defined as one of the simplest methods of reversible
immobilization which involves the enzymes being physically adsorbed or attached
to the nonreactive support material (Sakai et al. 2010; Es et al. 2015). It is easy to
perform, and moreover, it preserves the catalytic activity of the enzyme (Mohamad
et al. 2015). Entrapment can be defined as the physical restriction of an enzyme
within a network or a confined space. It is an irreversible method of immobilization
wherein the enzymes are entrapped in a lattice structure of fibers or in polymer
membranes which allow the movement of substrate and products across the
Fig. 5 The major techniques used for the immobilization of microbial enzyme for degradation
studies: (a) physical adsorption, (b) encapsulation, (c) covalent bonding, (d) cross-linking,
(e) entrapment
membrane but retain the enzyme (Wang and Zhang 2015; Beloqui et al. 2016).
Cross-linking is an irreversible method of enzyme immobilization that does not
require a support as the enzyme acts as its own substrate. It is also known as carrier-
free immobilization and copolymerization (Sirisha et al. 2016). In this method,
virtually pure enzymes are obtained by eliminating the advantages and disadvan-
tages associated with carriers (Datta et al. 2013). Covalent bonding is one of the most
widely used methods for irreversible enzyme immobilization, and it mainly depends
on the formation of covalent bond between the enzyme and the support material
(Sirisha et al. 2016). Covalent bond formation between the enzyme and the matrix
occurred through the side-chain amino acids like cysteine (thiol group), lysine
(ε-amino group), and aspartic and glutamic acids (carboxylic groups) (Mohamad
et al. 2015). Covalent bonds provide powerful linkages between the lipase and its
carrier matrix allowing its reuse more often than with other available immobilization
methods and prevent enzyme leakage into the environment.
In a study conducted by Datta et al. (2013), immobilization of microbial lipase
from Yarrowia lipolytica onto octyl-agarose and octadecyl-sepabeads supports by
physical adsorption resulted in higher stability (tenfold) and better yield than that
of free lipase. Similarly, lipase from Candida rugosa physically adsorbed onto
biodegradable poly(3-hydroxybutyrate-co-hydroxyvalerate) exhibited 94% resid-
ual activity at 50 C after 4 h and reusability till 12 cycles (Datta et al. 2013).
Likewise, in a dual-enzyme reaction system composed of a polyester hydrolase and
an immobilized carboxyl esterase TfCa from Thermobifida fusca KW3, a twofold
higher yield of biodegradation end products was reported by Barth et al. (2016).
Similarly, the use of immobilized cells for a mechanical size reduction in the
polyurethane foam has been suggested by Cregut et al. (2013). However, an
efficient biocatalytic degradation approach using immobilized cells for polyethyl-
ene has not yet been demonstrated.
Scope of Bioinformatics and Computational Biology
The bioremediation of xenobiotic compounds either ex situ or in situ by individual

isolates does not represent the actual behavior of microorganisms; however, it
depends on cooperative metabolic activities of microbial consortia (Khan et al.
2013). Hence, in silico analysis helps in predicting the fate of a compound by all
microorganisms for either partial or complete degradation to nontoxic compounds
(Arora and Bae 2014). Similarly, several computational tools and databases have been
developed to assist the design and implementation of microbial consortia for envi-
ronmental site remediation and hazardous waste management (Fulekar and Sharma
2008). These may include biodegradation databases, chemical toxicity prediction
systems, and biodegradation pathway prediction systems (Arora and Bae 2014). It
must be noted that the huge amount of data generated by computational analysis
needs validation to better understand the biodegradation potential of a compound by
microorganisms in the environment. Further, the pathway prediction systems and
phylogenetic analysis will help in minimizing the number of possible combination
required for the development of novel microbial consortia (Khan et al. 2013).
Biodegradation Databases
Biodegradation databases store information related to biodegradation of chemicals

including xenobiotic-degrading bacteria, metabolic degradation pathways of toxic
chemicals, and enzymes and genes involved in the biodegradation (Arora and Bae
2014). These databases include the biodegradation network-molecular biology data-
base (Bionemo), University of Minnesota Biocatalysis/Biodegradation Database
(UM-BBD), BioCyc, and MetaCyc (Arora and Bae 2014).
Biodegradation Network-Molecular Biology
Biodegradation network-molecular biology database (Bionemo) is a manually

curated database that provides information pertaining to proteins and genes involved
in the biodegradation metabolism (Carbajosa et al. 2009). It was developed by the

Structural Computational Biology Group at the Spanish National Cancer Research
Centre, and it can be freely accessed at https://bionemo.bioinfo.cnio.es. Bionemo
links sequence database entries to biodegradation reactions by the information
retrieved from published research articles. The database comprises of 234 microbial
species, 1107 proteins, 212 transcription units, 90 transcription factors, 945 reactions,
537 enzymatic complexes, and 145 biochemical pathways (Carbajosa et al. 2009;
Shah 2017). Like other databases, Bionemo is also cross-linked to GenBank for
DNA sequences, UniProt for protein sequences, NCBI Taxonomy for microbial
species, UM-BBD for metabolic reactions, and PubMed for references (Gao et al.
2010). The information available in the Bionemo database may aid in primer design,
for cloning experiments, and directed evolution experiments. The complete database
can also be freely downloaded from PostgreSQL (https://www.postgresql.org/).
University of Minnesota Biocatalysis/Biodegradation Database
The University of Minnesota Biocatalysis/Biodegradation Database (UM-BBD) is a

widely used database in the field of biodegradation, and it is freely available at http://
eawag-bbd.ethz.ch/. This database provides information regarding microbial biocat-
alytic reactions, enzymes, genes, and biodegradation pathways involved in biore-
mediation (Gao et al. 2010). The metabolic pathways of various xenobiotic
compounds are available in text and graphical formats. These manually annotated
metabolic pathways display multistep enzymatic reactions in a series initiating from
the starting compound. Currently, the UM-BBD database includes 543 microbes,
993 enzymes, 1503 chemical reactions, and 219 microbial degradation pathways
which are cross-linked to several other databases including NCBI (https://www.ncbi.
nlm.nih.gov/), BRENDA (http://www.brenda-enzymes.org/), ExPASy (http://www.
expasy.org/), and ENZYME (http://enzyme.expasy.org/) to provide vital information
describing genes and enzymes involved in the biodegradation of xenobiotic com-
pounds (Shah 2017). Additionally, this database includes a Biochemical Periodic
Table (UM-BPT) and a rule-based Pathway Prediction System (UM-PPS) that pre-
dicts plausible pathways for microbial degradation of organic compounds (Gao et al.
2010). UM-BBD compound data are also linked to public chemical databases such
as PubChem and ChemSpider.
MetaCyc and BioCyc
MetaCyc database is a collection of experimentally elucidated metabolic pathways

and enzymes highly curated from primary scientific literature from all domains of
life (Caspi et al. 2016). MetaCyc is currently the largest collection of metabolic
pathways with more than 2400 pathways derived from more than 46,000 publica-
tions. It comprises of 2526 experimentally determined metabolic pathways from
more than 2844 different organisms (Shah 2017). This database hosts metabolic
pathways involved in both primary and secondary metabolisms in addition to

enzymes, reactions, metabolites, and genes involved for metabolism (Caspi et al.
2016). This database is freely accessible at http://metacyc.org/. In addition to being
an online repository of metabolism, other scientific applications of MetaCyc include
computational prediction and comparison of the metabolic pathways in sequenced
genomes, information pertaining to metabolic engineering through enzyme data-
base, and aid in metabolomics research (Caspi et al. 2016).
BioCyc database is a collection of 5700 organism-specific Pathway/Genome
Databases (PGDBs). The complete genome and predicted metabolic network of
one organism, including metabolites, enzymes, reactions, metabolic pathways, pre-
dicted operons, transport systems, and pathway-hole fillers, can be visualized (Caspi
et al. 2012). The Pathway Tools software in BioCyc predicts metabolic pathways
using MetaCyc as a reference database (Caspi et al. 2016). Further, this database
offers multiple tools for querying and analyzing PGDBs for the comparative analysis
of gene expression and metabolomics data using Omics Viewers and genome
browsers (Karp et al. 2015). This database is freely accessible at https://biocyc.
org/. Recent developments of the database include addition of Gibbs free energy
values for compounds and reactions, the addition of a tool for creating diagrams
containing multiple-linked pathways, new search capabilities for searching genes
based on organism’s phenotypes, sequence patterns, and a metabolite identifier
translation service (Caspi et al. 2012). Recent PGDB additions to BioCyc database
over the past 2 years include YeastCyc (Saccharomyces cerevisiae), EcoCyc
(Escherichia coli) (Karp et al. 2014), HumanCyc (Homo sapiens) (Romero et al.
2004), and BsubCyc (Bacillus subtilis). MetaCyc and BioCyc are curated and
maintained by researchers at SRI International. These databases aid in the selection
of a particular microorganism for the biodegradation of xenobiotics.
Computational Biology Resources for Pathway Prediction
PathPred
PathPred (Moriya et al. 2010) is a knowledge-based web server that predicts possible
enzyme-catalyzed reaction pathways of a query compound by information retrieved
from the KEGG REACTION (Muto et al. 2013) and KEGG RPAIR databases
(Oh et al. 2007). The KEGG REACTION database contains all the reactions taken
from the KEGG metabolic pathways in addition to known enzymatic reactions
retrieved from the IUBMB enzyme nomenclature. Similarly, KEGG RPAIR is a
collection of biochemical structure transformation patterns (RDM patterns) for
substrate-product pairs (reactant pairs) in KEGG REACTION (Muto et al. 2013).
This web server provides plausible reactions and transformed compounds and
displays all possible predicted reaction pathways in a tree-shaped graph (Moriya
et al. 2010). An end product/compound can be queried in three different ways, either
in the SMILES representation or the MDL mol file format or directly by the help of
KEGG compound identifier (Moriya et al. 2010). The pathway prediction results are
also linked to the genomic information. This web server displays new and alternative
reactions irrespective of whether enzymes for these reactions are present or not. If the
enzyme is nonexistent, users can use the enzyme tool (http://www.genome.jp/tools/
e-zyme/) to assign a possible EC number. PathPred web server can be freely
accessed at http://www.genome.jp/tools/pathpred/. It is currently maintained by
Kyoto University Bioinformatics Center.
Biochemical Network Integrated Computational Explorer
Biochemical Network Integrated Computational Explorer (BNICE) is a computa-

tional approach for the development of novel pathways based on the reaction rules of
the Enzyme Commission classification system (Finley et al. 2009). Initially, this
approach checks for all possible metabolic pathways from a given user-specific
target or starting molecule. Further, it filters out all possible pathways for thermo-
dynamic feasibility based on the Gibbs free energies of the reaction and then selects a
feasible unique thermodynamic pathway (Finley et al. 2009). These generated
pathways can be further assessed using existing pathway analysis systems, such as
thermodynamics-based flux balance analysis (FBA) that allows investigation of the
overall effects of these novel pathways on metabolic network performance in host
organisms (Soh and Hatzimanikatis 2010). FBA aids in the prediction of phenotypic
changes, changes in bioenergetics of the system for metabolic engineering, effects of
gene knockouts, and biodegradation of xenobiotics. Major applications of BNICE
include discovery and analysis of novel metabolic pathways, evolutionary analysis
between metabolic pathways of various organisms, and analysis of degradation
pathways of xenobiotic compounds (Finley et al. 2009).
From Metabolite to Metabolite
From Metabolite to Metabolite (FMM) predicts metabolic pathways form one

metabolite to another metabolite among different species mainly based on the
Kyoto Encyclopedia of Genes and Genomes (KEGG) database and other integrated
biological databases (Chou et al. 2009). It is a freely available web server that can be
accessed at http://FMM.mbc.nctu.edu.tw/. FMM generates combined metabolic
pathways by combining the information available in KEGG PATHWAY and
KEGG LIGAND databases (Muto et al. 2013). This web server also provides
information regarding the corresponding enzymes, genes, and organisms for com-
parative analysis, in which metabolic pathways can be compared between numerous
species. FMM is an efficient tool in the field of synthetic biology and metabolic
engineering. For biodegradation studies, metabolic pathways (both local and global
graphical maps) of xenobiotic compounds can be searched and visualized (Chou
et al. 2009). FMM provides a highly effective way to elucidate the genes (from
which species) should be cloned into the microorganisms for increased metabolite
production based on comparative analysis.
Metabolic Tinker
A recently developed web tool, Metabolic tinker (McClymont and Soyer 2013),
can be employed to design synthetic metabolic pathways between an end product
(user-defined target) and source compounds. Metabolic tinker uses a tailored
heuristic search approach to return a large number of thermodynamically feasible
paths in the entire known metabolic universe owing to its broad search base.
Metabolic tinker is a freely available web service which can be accessed at http://
osslab.ex.ac.uk/tinker.aspx. The same website also provides the source code,
allowing it to be developed further or run on personal machines for specific
applications. The program contains a directed graph known as Universal Reaction
Network (URN), which represents the entire set of known compounds and reac-
tions from the ChEBI and Rhea databases (McClymont and Soyer 2013). Edges
and nodes on this graph represent reactions and metabolites, respectively. Meta-
bolic tinker searches possible biochemical pathways between two compounds
within this URN using standard search algorithms developed in computer science
and graph theory. Existing tools do not incorporate the search for compound
similarity and thermodynamic stability in searching natural pathways defined in a
specific species context; hence, Metabolic tinker is an important tool for the
prediction of metabolic pathways.
MetaRouter
MetaRouter is a system that maintains heterogeneous information related to biore-

mediation and biodegradation pathways. The core of this system is a relational
database where the information on reactions, chemical compounds, enzymes, and
organisms is stored in an integrated framework (Pazos et al. 2005). The current set of
data includes 740 compounds, 502 enzymes, 820 reactions, and 253 organisms
(Pazos et al. 2005; Shah 2017). It is currently linked to major public databases
such as ENZYME (http://enzyme.expasy.org/), UM-BBD (http://eawag-bbd.ethz.
ch/), Swiss-Prot (http://www.uniprot.org/), and Protein Data Bank (http://www.
rcsb.org/pdb/). Although, MetaRouter system does not provide information regard-
ing kinetics or thermodynamics of the proposed pathways, it aids in assessing the
environmental fate of harmful compounds and in designing biodegradative strategies
for the same (Hatzimanikatis et al. 2005; Khan et al. 2013). It is freely available at
http://pdg.cnb.uam.es/biodeg_net/MetaRouter.
Other pathway prediction systems include Metabolic Route Explorer (MRE)
(http://www.cbrc.kaust.edu.sa/mre/) (Kuwahara et al. 2016), Metabolic Route
Search and Design (MRSD) (http://bioinfo.ustc.edu.cn/softwares/mrsd/) (Xia et al.
2011), eXTended Metabolic Space (XTMS) (http://xtms.issb.genopole.fr)
(Carbonell et al. 2014), CarbonSearch (http://www.kavrakilab.org/atommetanet/)
(Heath et al. 2010), GEM-Path (Campodonico et al. 2014), MetaRoute (http://
www-bs.informatik.uni-tuebingen.de/Services/MetaRoute) (Blum and Kohlbacher

2008), and AGPathFinder (http://210.36.16.170:8080/AGPathFinderWeb/login.jsp)
(Huang et al. 2017).
Protein Structure Prediction
Protein structure prediction programs predict three-dimensional structures of the

proteins that have not been experimentally elucidated and deposited in structural
databases. Three-dimensional structure of an enzyme is essential for computational
analysis such as molecular docking and molecular dynamic simulations. In some
cases, when a three-dimensional structure of the enzyme of interest is unavailable in
its native form, the 3D structure of the protein can be predicted by computational
biology tools. There are three approaches for protein structure prediction, namely,
homology modeling, fold recognition, and ab initio approaches.
Homology Modeling
Homology modeling is predicting an atomic resolution model of the “target” protein

(protein of interest) from its amino acid sequence and an experimental 3D structure
of a related homologous protein of the “template” (Lee et al. 2009). It is also known
as comparative modeling. It has been reported that the protein structures are highly
conserved than protein sequences amongst homologues, but sequences falling below
a 30% sequence identity can have different structures. Similarly, naturally occurring
homologous proteins have similar protein structures, and evolutionarily related pro-
teins have similar sequences. The quality of the predicted homology model is
dependent on the quality of the sequence alignment and template structure. The
major steps involved in homology modeling include target retrieval, template iden-
tification, target-template alignment, model prediction, loop modeling, side-chain
refinement, model refinement, and validation (Lee et al. 2009).
Fold Recognition
Fold recognition, also known as protein threading, is a method of structure predic-

tion which involves proteins that have the same fold as proteins deposited in the
structural databases but are not homologous in nature (Kelley et al. 2015). It differs
from the homology modeling method of structure prediction as it is used for proteins
which do not have their homologous protein structures deposited in any of the
structural databases. The prediction is carried out by aligning each amino acid in
the target sequence to a position in the template structure and evaluating how well
the target fits the template. Homology modeling and protein threading are both
template-based methods (Lee et al. 2009).
Ab Initio Method
Ab initio or de novo methods predict a 3D structure directly from the primary

sequence, without the need for a template. De novo techniques are much more
computationally intensive than template-based methods and usually limited to
smaller proteins (<100–120 residues) (Hung et al. 2007). There are two components
to ab initio prediction: devising a scoring (i.e., energy) function that can distinguish
between correct (native or native-like) structures from incorrect ones and a search
method to explore the conformational space (Hung et al. 2007). It has been reported
that template-based methods are more accurate than ab initio methods for protein
structure prediction (Lee et al. 2009).
These predicted structures can be validated and further explored for docking
studies. A plethora of online web servers and stand-alone programs are available for
both prediction and validation of predicted 3D structures. Commonly used tools/web
servers for protein structure prediction include MODELLER (Webb and Sali 2016),
I-TASSER (Yang et al. 2015a), HHpred, SPARKSx, QUARK, RaptorX, Phyre, and
Phyre2 web server (Kelley et al. 2015). These predicted 3D structures can be
evaluated using several tools and web servers such as ProCheck, WHATIF,
ERRAT, PROVE, ANOLEA, Verify3D, DSSP, ProMotif QMEAN, and ProSA
(Meier and Soding 2015).
Molecular Docking Analysis
Molecular docking studies help in displaying the potential ability of an enzyme to

adhere to the pollutant and its functionality in the process of biodegradation (Fisher
et al. 2014). There are two kinds of molecular docking procedures involving either a
flexible-body docking where the ligand and target are allowed to rotate along
multiple degrees of freedom or rigid-body docking where both ligand and target
are stationary during the process. These analyses further assist in understanding
whether the active site of certain enzymes can accommodate the polluting compound
or not, based on the nature of binding pocket and stearic hindrance of the residues
(Basharat et al. 2017). Similarly, the protein-pollutant interactions can be studied by
assessing thousands of potential docking conformational poses generated using
softwares such as AutoDock Vina, Glide, SwissDock, PatchDock web server,
FlexX, FTDock, GEMDOCK, GOLD, Schrödinger, iGEMDOCK, YASARA, and
DARWIN (Schneidman-Duhovny et al. 2005; Friesner et al. 2006; Trott and Olson
2010; Grosdidier et al. 2011).
In our recent study, the molecular interactions between microbial lipase of
Pseudomonas spp. and two forms of plastic (polyethylene and polystyrene) have
been illustrated using PatchDock web server (Skariyachan et al. 2015). Similarly,
Vieira et al. (2015) investigated the potential application of the fungus Ceriporiopsis
subvermispora in degrading the xenobiotic compound diuron (herbicide) by means
of molecular docking studies using the modeled structure of enzyme laccase-1 as the
target.
Molecular Dynamic Simulations
The major drawback of molecular docking studies is that the protein is held static
during the analysis (Fisher et al. 2014). This can be overcome by another computa-
tional method known as molecular dynamic simulations. Proteins that undergo
significant conformational changes during docking studies are further studied by
molecular dynamic simulations (Ferreira et al. 2015). Similarly, when a 3D structure
for a particular target is unavailable or the binding sites are poorly defined, molecular
dynamics can be applied to generate a set of reliable structures for docking analysis
(Salsbury 2010). Molecular dynamic simulations help in estimating the stability of a
ligand-receptor complex proposed by molecular docking studies (Ferreira et al.
2015). It allows both enzyme and ligand(s) to alter their conformations in the
complex during a biological process (Fisher et al. 2014). Molecular dynamic simu-
lation studies make use of the most popular force fields such as GROMACS
(Abraham et al. 2015), NAMD (Phillips et al. 2005), AMBER (Case et al. 2017),
and CHARMM (Brooks et al. 2009). These studies can be carried out using pro-
grams such as Abalone, Amsterdam Density Functional (ADF), Large-scale Atomic/
Molecular Massively Parallel Simulator (LAMMPS), and Desmond (Lindorff-
Larsen et al. 2010). Similarly, specific molecular dynamic simulations can also be
performed to generate information about the structure of the enzyme and the active
site analysis for ligand binding (Fisher et al. 2014). The results obtained from these
simulations provide significant insights toward the catalytic activity of microbial
enzymes on various forms of polymeric hydrocarbons such as polyethylene. Molec-
ular dynamic simulations and docking studies accelerate the procedure of screening
and improving enzymatic properties of an enzyme for a particular pollutant by
providing a better understanding of the reaction mechanism (Basharat et al. 2017).
Knowledge derived from molecular dynamic simulations and docking studies are
crucial in designing strategies for measures aimed at environmental site remediation
and hazardous waste management.
Conclusion
The degradation of plastic through biotechnological intervention should be consid-

ered of utmost importance in the current fields of study. The different types of
microorganisms present in ecosystem play a vital role in plastic degradation. The
formation of biofilms on surface of plastic polymers and production of biosurfactant
by microorganisms will enhance the degradation rate of major plastic polymers such
as polyethylene. Formulating novel microbial consortia will aid in polyethylene
degradation at a faster rate than individual isolates by producing extracellular

enzymes which break down complex polymers into monomers making it more
permeable. The application of novel microbial consortia will provide environmental
site remediation and hazardous waste management for biodegradation of low- and
high-molecular-weight polyethylene and related polymers. Computational biology
resources play a vital role in the analysis of degradation end products and the
prediction of probable mechanisms and metabolic pathways followed by the micro-
bial consortia during biodegradation.
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Micro-remediation of Metals: A New
Frontier in Bioremediation 19
A. Banerjee, M. K. Jhariya, D. K. Yadav, and A. Raj
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 480
Metals in the Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
Principles Behind Microbial Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
Mycoremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
Cyanoremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
Biostimulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
Biomineralization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
Biosorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
Molecular Mechanisms Involved in Bioremediation Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
Microbes Involved in Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
Bioremediation by Microbes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
Plant Growth-Promoting Bacteria (PGPB) Mediated Decontamination of
Heavy Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 491
Metal-Microbe Interaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 492
Microbes and Metal Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 495
General Mechanism of Metal Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 495
Metal-Dependent Mechanism of Metal Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 496
Microbial Resistance to Oxyanions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
Resistance to Divalent Metal Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
Microbial Transformations of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
Mechanisms of Metal Transformation by Microbes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
Biologically Catalyzed Immobilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
Biologically Catalyzed Solubilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
Microbial-Assisted Phytoremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
Designer Microbes Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
A. Banerjee (*)
Department of Environmental Science, Sarguja University, Ambikapur, Chattisgarh, India
M. K. Jhariya · D. K. Yadav
Department of Farm Forestry, Sarguja University, Ambikapur, Chattisgarh, India
A. Raj
Department of Forestry, College of Agriculture, I.G.K.V, Raipur, CG, India

https://doi.org/10.1007/978-3-319-73645-7_10
480 A. Banerjee et al.
Rhizosphere Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503

Manipulation of Plant-Microbe Symbiosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
Future Prospects: Microbial Remediation and Its Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 504
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 506
Abstract
Microbial remediation is an innovative technique which aims toward decontam-
ination of polluted sites through metal immobilization. This approach would
make lesser availability of heavy metals to living system. It was found that
precipitation and transformation through metabolic activity of microbes are
very much useful in this context. Such process reduces the hazards of metal
pollution. Use of living organisms for decontamination of pollutions has got
holistic approach including various microbes, algae, fungi, higher plant process
known as bioremediation. From microbes perspectives, various processes such as
promoting indigenous microbial population for decontamination, exogenous
input of microbes for decontamination purpose, utilization of microbial strain
for sequestering pollutants as well as metal immobilization through microbial
biomass are available. Metals have diverse source of contamination by anthro-
pogenic mode. Metal biotransformation is the principle mechanism of microbial
remediation for decontaminating environment. It involves processes such as cell
membrane transport, physical adsorption, and ion exchange complexation and
biosorption. Diverse microbial groups such as plant growth-promoting
rhizobacteria or PGPR actively participate in metal decontamination process.
Metal-microbe interaction for heavy metal removal includes processes such as
bioleaching, bioaccumulations biotransformation, biomineralization, and
biosorption. Metal resistance of microbes involves expolymer binding,
siderophore and biosurfactant complexation, metal precipitation, and metal-
dependent mechanism of metal resistance. Biotransformation of metal cations
involves bacterial cell-mediated biologically catalyzed immobilization and solu-
bilization process by diverse group of microbial community.
Keywords
Bioremediation · Interaction · Micro-remediation · Metal · Microbes
Introduction
Bioremediation is a technology that uses metabolic processes to degrade or trans-

form contaminants, so that they remain no longer in harmful form. In some cases, the
contaminant is the primary part of the metabolic process, acting as a main source of
carbon and energy for the microbial cell. In others, it is transformed into a second
substance and serves as a primary energy or carbon source. This co-metabolism
process may be purely fortuitous, and the microorganism gains nothing from the
process. In the case of metals, it is only the biotransformation process that was
exploited widely as a bioremediation strategy. After the use of super bug in cleaning
19 Micro-remediation of Metals: A New Frontier in Bioremediation 481
up oil spills, there have been numerous successful stories of bioremediation tech-
nique in the cleanup of vast areas of contaminated environments (USGS 1997).
Microbial bioremediation can be defined as a mechanism by which microbes tend
to degrade the hazardous organic contaminants below the safe limit in various
segments of environment (Gareth and Furlong 2003). The main mechanism behind
this biodegradation process involves enzymatic transformation of materials and
subsequently deriving energy from the degraded product. Conversion of larger
molecules into smaller one is the main theme of such biodegradation. For water
and wastewater treatment, the microbial response with reference to toxicants is of
prime importance. It was observed that microbial metabolites may be innocuous or
valuable in nature in terms of its applicability (Gupta et al. 2000).
In the aquatic environment, microbes play a significant role in metal decontam-
ination from water. As for example in various wastewater treatment systems, bacteria
play the pivotal role in degradation of sewage effluent. In a wastewater treatment
plant, microbial community resides in slurry bioreactors and biodegrades and
biotransforms various solid compounds. Microbes performing such functionality
require nutrient and optimum environmental conditions. Wastewater treatment sys-
tem includes a wide array of microbes providing specific functions of biodegrada-
tion. Each species has its own ecological amplitude with reference to various abiotic
factors which regulate their growth and development.
During recent times, metal-microbe interaction happens to be the most interesting
topic. Most of the earlier researches have focused on exploring the mechanisms and
processes associated with metal resistance through microbes (Ezzouhri et al. 2009).
Active and passive absorption of heavy metals has been reported earlier (Das et al.
2008). Biosorption happens to be more promising than bioaccumulation. Organisms
required nutrients for their growth and development and subsequently uptake oxy-
gen and promotes higher level of chemical oxygen demand (Hussein et al. 2005).
Bioaccumulation seems to be the promising technology for metal decontamination
from a contaminated habitat (Rani 2009).
Research reports reveal microbial community reflects higher level of resistance
toward high level of heavy metal concentration present in effluents. Microbial com-
munity happens to be of significant versatility in terms of heavy metal bioremediation
and is therefore very much fruitful in terms of environmental cleanliness. Different
efforts have been made in the field of metal recovery at various concentrations.
This chapter focuses on the role of metal-microbial relationships, microbial
processes governing bioremediation, and various techniques available for metal-
contaminated sites. This chapter also throws light on bioremediation techniques used
exclusively for chromium-contaminated soils and possible future developments in
the field of bioremediation.
Metals in the Environment
Throughout the world, the soil environment gets polluted through natural rock
disintegration and weathering as well as other various forms of anthropogenic
inputs. Ross (1994) reported five different dimensions of metal inputs in soil. Source
includes mining activities, industrial activity, air inputs, cultivation practices, and
pollution from waste materials. As per research reports, phenomena such as atmo-
spheric fallout contribute significantly toward heavy metal deposition (Purakayastha
and Chhonkar 2010). From an Indian perspective, industry and improper waste
disposal is the major root cause of contamination of soil. From various research
reports, it is evident that heavy metals and metalloids are mostly associated with
environmental pollution and contamination (Cao et al. 2014). Contaminations
spread from mining, smelting, electroplating, production of coal oil natural gas
and energy, synthetic fertilizers, other agrochemicals, etc. (Purakayastha and
Chhonkar 2010; Ma et al. 2011). Non-biodegradable nature leads to hyper-
accumulation of these compounds into various segments of the environment
(Kumar Sharma et al. 2007). Contamination of the environment in various dimen-
sions worldwide has necessitated the importance of bioremediation technology for
human sustainability (Mulligan et al. 2001a; Lado et al. 2008).
Table 1 represents the visible symptoms of various heavy metals in plants. In the
case of most of the heavy metals, necrosis and chlorosis of the plant body are the
common symptoms. This therefore indicates that various heavy metals have signif-
icant effect upon plant system, and if properly not decontaminated, they can cause
diverse nature of injury to the living entity of the ecosystem. Heavy metals have their
impact on every plant part. This necessitates the exploration of different bioremedi-
ation techniques to combat such problems.
Figure 1 represents the source of origin and distribution of heavy metals in every
sphere of the environment. The mobilization of heavy metals within the environment
can be natural and anthropogenic. Anthropogenic sources display a wide array of
heavy metals in various segments. Among the various anthropogenic activities,
industry and agriculture are the two key events that are driving the humankind.
These two activities provide the source of contamination of Cd, Cu, Pb, Zn, and
As. Mining involves the contamination of Hg, Pb, As, and Cd. This therefore
necessitates the development of suitable bioremediation process and technology
Table 1 Visible symptoms of metal phytotoxicity

Metal Symptoms Sources
Zinc Chlorosis in leaves and limited shoot growth Ebbs and
Kochian (1997)
Copper Interveinal chlorosis, necrosis of leaf tips, stunted shoot and Gunawardana
root growth et al. (2010)
Cadmium Chlorosis, wilting stems, stunted shoot and root growth, Pandey and
red/purple leaf veins, and petioles Sharma (2002)
Lead Stunted leaf growth with dark-green leaves and reduced root Gunawardana
elongation et al. (2010)
Manganese Chlorosis of leaf margins, leaf abscission, loss of apical El-Jaoual and
dominance, root growth inhibition, and progressive browning Cox (1998)
of roots from tips
Nickel Progressive chlorosis, necrosis of young leaves and shoot Pandey and
apex, and increase in red pigmentation Sharma (2002)
Anthropogenic sources
of metal contamination
Industry
(Cd, Cr, Co, Cu, As, Ni, Atmospheric deposition
Zn, Hg) (Pb, Cu, Cr, Cd, Hg, As)
Waste disposal Agriculture

(Cd, Cr, Cu, Pb, Hg, Zn) (Cd, Cu, Pb, U, Se, Zn,
As)
Mining and Smelting

(Hg, Pb, As, Cd)
Fig. 1 Contamination of soil through heavy metal by anthropogenic activity
along with potential bioremediating agents for effective decontamination of

environment.
Micro-remediation processes are effective only under congenial environment for
microbes, i.e., conditions favorable for microbial growth. From the research reports,
it appears that heavy metal-tolerant microbes are well adapted with other abiotic
factors but are metal specific in remediation. Problems lie within the fact that some of
the metals are non-biodegradable and biodegradable ones have slow degradation rate
(Vidali 2001).
Principles Behind Microbial Remediation
Continuous increase of anthropogenic influence over earth’s natural processes has

led to perturbances in the form of environmental degradation. It is associated with
higher accumulation of environmental contaminants and other toxicant materials.
Under this purview, proper treatment technology needs to be designed for existence
of humankind. From the very beginning of life, it was observed that microbes are
omnipresent over the earth’s surface. Not only their presence but also their indige-
nous capability has led them to be considered as the friend of lithospheric elements.
They have inherent capacity to survive under any form of stress condition as well as
undergo biotransformation of compound present in air, water, and soil (Fredrickson
and Onstott 1996). Typically they have sufficient area for biochemical reaction (Fein
et al. 1997). According to research, an estimated 1 g of soil harbors 106–1010 cfu
(colony-forming units) (Barns and Nierzwicki-Bauer 1997). Physical and chemical
methods of remediation are often found to be unsustainable from an environmental
perspective and cannot be adopted at wider scale due to high cost (Mulligan et al.
2001a). Therefore, micro-remediation, i.e., using microbes for remediating contam-
inated and polluted environment, is a suitable alternative present in our hand.
Metal transformation by microbes is a very crucial factor due to its wide appli-
cability. The principle mechanisms involved are transformation of inorganic forms
through redox reaction as well as simple conversion between inorganic and organic
forms (Tebo et al. 1997). Cellular metabolic activity often has a significant role in
metal biotransformation through metal reduction as a part of anaerobic respiration
(Lovley and Coates 1997). Such reductional activity in microbial cell often imparts
metal resistance among microbes. Metal reduction through changes in oxidation
number of different elements is very frequent in nature such as reduction of chro-
mium from +6 to +3 state (Ramasamy 2000), reduction of selenium from +6 to
0 state (Lloyd et al. 2001), reduction of uranium from +6 to +4 state (Chang et al.
2001), and reduction of mercury from +2 to 0 state (Brim et al. 2000). It has been
observed that methylated product of microbes appears to be volatile in nature.
From the incidence of Minamata disaster in Japan, it was observed that different
bacterial species have the capability for microbial conversion of inorganic mercury
into methylated form of mercury (Pongratz and Heumann 1999). Biomethylated
mercury appears to be the most toxic form of mercury in terms of its persistancy in
the environment (Nikunen et al. 1990). Biomethylation phenomenon is very much
common in other cases such as conversion of arsenic to gaseous arsines (Gao and
Burau 1997), selenium to volatile dimethyl selenide (Dungan and Frankenberger
2000), and lead to dimethyl lead. Acidophilic and oxidizing-type bacteria such as
iron and sulfur bacteria can mobilize higher amounts of metal, metaloid, and
micronutrients from the degraded environment. Research reports reveal sulfur-
reducing bacteria can precipitate metal through cellular metabolism using sulfate
and organic matter as substrate molecule (White et al. 1997). Such biotransformation
process which includes increasing bioavailability, toxicity of metal, or metal immo-
bilization acts as a key process in geochemical cycling of metals in metal-
contaminated sites (Lloyd and Lovley 2001).
Inherent mechanism such as sorption, accumulation, enzymatic reduction, and
immobilization by microbial biomass reflects the wide dimension of metal-microbe
interaction (Ramasamy et al. 2007). Metal uptake within the cell is a phase-wise
mechanism. Metal transfer across cellular membrane is associated with cellular
metabolism in viable cells. This is a part of inherent microbial defense system
which becomes functional under metal toxicity. Non-metabolic mode of transport
involves chemical interactions between metal and functional group of the cell
surface of microbial cell. Processes include sorption of chemical compound, ion

exchange mechanism, and adsorption.
Metal precipitation can take place both under soil solution and at the surface level
(Ercole et al. 1994). It involves bimodal activity in which one includes production of
chemical compounds by the bacterial cell to favor precipitation and the other takes
place through interrelationship between metal and bacterial cell surface through
chemical means. It includes different processes such as transportation of metal
ions across the cell membrane through adsorption and intercellular transport of
metal ion.
Physical adsorption takes place through elactrostatic interactions between solu-
tion and cell wall of bacteria (Kuyucak and Volesky 1988). Ion exchange mechanism
involves exchange of metal ion between organic compound such as polysaccharides
and bivalent ions of the microbial cell and heavy metal present in the environment.
Complexation includes chemical reactions between metal and microbial cell and
leads to complex formation by coordination bond formation. Biosorption involves
ionic equilibrium mechanisms as well as surface complexation models. Several
workers have reported that the ionic nature of bacterial cell wall helps in metal
absorption process (Vijayaraghavan and Yun 2008).
Biotransformation is an effective process under bioremediation to detoxify heavy
metal contaminants. Fungi have shown significant promise in this field of biotrans-
formation (Pinedo-Rivilla et al. 2009). Several fungal populations, viz.,
Allescheriella sp., Botryosphaeria rhodina, Klebsiella oxytoca, Phlebia
sp. Pleurotus pulmonarius, and Stachybotrys sp., have been reported to actively
participate in metal-binding process (D’Annibale et al. 2007). Fungal species such as
Aspergillus parasitica and Cephalosporium aphidicola have been reported to
actively remediate lead from contaminated site (Akar et al. 2007). Hymenoscyphus
ericae, Neocosmospora vasinfecta, and Verticillium terrestre have been reported to
convert toxic form of mercury into nontoxic form (Kelly et al. 2006). Uptake of toxic
contaminants which are hydrophobic in nature is mediated through bio-secretion of
surfactant molecules upon the toxicant as well as through direct cell uptake.
Biosurfactants were found to be effective in chemical binding with metals before
being released from soil matrix into soil solution due to low interfacial tension
(Thavasi 2011).
Bacterial species operate in two ways to decontaminate environment. One mech-
anism involves biotransformation, and the other mechanism involves effluxing toxic
metal from the cell (Silver 1996). The mechanism of oxidation and reduction takes
place between metal and microorganism in which microorganism happens to be the
oxidizing agent oxidizing heavy metal to nontoxic form. In this pathway the
electrons released were accepted by different anions present in soil environment.
Under anaerobic conditions, microbes act upon organic compounds by reducing
different anions which are electron acceptors (Lovley and Phillips 1988). Iron (III)
appears to be the stimulatory factors in this anaerobic degradation of organic
compounds (Spormann and Widdel 2000).
Microorganisms such as Geobacter species have been reported to convert soluble
uranium into insoluble form (Lovley et al. 1991). Diverse mechanisms such as efflux
of metal, segmentation, formation of complex compound, and biosynthesis of pro-

teins and peptide molecules help to reduce the toxic stress on the living cell (Gomez
Jimenez et al. 2011). Biosynthesis of proteins and peptide is useful for heavy metal
accumulation (Cobbett and Goldbrough 2002). These biomolecules are produced
through cell-signaling process under heavy metal stress (Kagi and Schaffer 1988).
One such example includes regulation of smtA gene in Synechococcus sp. which
leads to synthesis of metal-binding protein (Huckle et al. 1993). Research reports
reveal genetically modified species codes for metal-binding protein which reduce
heavy metal contamination from the contaminated environment (Valls et al. 2000).
Cadmium accumulation is mediated through protein and peptide biosynthesis by
Escherichia coli (Mejare and Bulow 2001). As per earlier research reports, glutathi-
one and phytochelatins promote twofold increase in cadmium accumulation (Kang
et al. 2007). Metalloregulatory proteins have been reported to regulate mobilization
of heavy metals into microorganisms (Singh et al. 2008).
Bioaccumulation is a process which involves movement of heavy metal from
outer surface of the cell within the cell cytoplasm (Ramasamy et al. 2007). It is very
much similar to the mechanism of nutrient uptake by microorganism. In this
mechanism firstly metal ions get adsorbed on the cell surface and then heavy metals
slowly enter into the cell cytoplasm. As a result the metal species get immobilized
within the cell cytoplasm – a process often designated as metal sequestration (Mishra
and Malik 2013). Enzymatic reduction and immobilization include transformation of
soluble form of metal with low oxidation state into insoluble form with higher
oxidation state. Bioventing involves application of nutrients and other supplements
into the contaminated sites to promote optimum growth of bacterial species which
can degrade diverse nature of contaminants. Mostly indigenous aerobic bacteria are
being effectively utilized during this process.
Biosparging process includes input of oxygen in groundwater to provide oxic
condition for biodegradation of contaminants through indigenous microbes (Adams
and Reddy 2003). Mixing of oxygen takes place in saturated zone which promotes
better contact between groundwater and soil. This is a very effective mode of
decontamination of soil and water from petroleum hydrocarbon compounds at
underground conditions (USEPA 2004). Bioprecipitation is such an approach
which includes chemical interaction between bacteria and toxic contaminants.
Under stress conditions, bacterial cells produce metal-adsorbing materials which
undergo chemical interaction with the toxic contaminants leading to its precipitation.
In bioaugmentation process, the strategies include application of previously
cultured microorganisms who can take active participation in degradation of toxic
contaminants into the contaminated sites. Source of the culture may be indigenous or
from outside (Tyagi et al. 2011). As per research findings, the interaction between
exogenous and endogenous culture is found to be negative. Exogenous inputs often
superimpose the indigenous populations in terms of their functionality, and therefore
loss of indigenous population becomes an inevitable fact. It has also been found that
under optimum condition of appropriate presence of indigenous microorganism,
biodegradation process remains highly effective (USEPA 2004). Combined appli-
cation of bioaugmentation and biostimulation along with necessary ingredients for
biodegradation in combination with kitchen waste or compost at 15–25% moisture

content and 30 2 C temperature appears to be effective (Cheng et al. 2009).
Some stimulants can be added in the contaminated site to provide optimum condition
of biodegradation for microbes. Such approach appears to be eco-friendly and good
option for environmental managers and bioremediating experts (EPA 2003).
Mycoremediation
Use of fungi to disintegrate the contaminants present in the environment and make it
pollution-free is a newer technology which is being widely used nowadays popularly
known as mycoremediation. Mycofiltration involves utilization of fungal mycelia as
a filtering medium for toxic contaminants and bacteria from soil solution through
microbial and enzyme activity. In mycoremediation different groups of fungi can be
effectively utilized in decontamination process. Fungal mycelium happens to pro-
duced extracellular enzyme and acids for biodegradation of lignin and cellulose
(Stamets 2005).
As per the reports of Dudhane et al. (2012), glomalin secretion promoted stabi-
lization of aluminum in soil and plant roots. Species like Aspergillus niger,
Aureobasidium pullulans, Cladosporium resinae, Funalia trogii, Ganoderma
lucidum, Penicillium spp., Rhizopus arrhizus, and Trametes versicolor have been
reported to perform metal recovery from contaminated environment (Say et al.
2003). Tastan et al. (2010) reported higher bioremediation potential through
bioaccumulation of chromium and copper molecule by Aspergillus versicolor
under pH 6. This therefore suggests that the concern species can be effectively
utilized as a bioremediating agent of chromium in contaminated sites. In a batch
sorption experiment, fungal species (Aspergillus fumigatus) were found to be
85.41% effective in removing lead from electronic wastewater (Ramasamy et al.
2011). In another experiment, Zeftawy and Mulligan (2011) reported higher rate of
filtration of heavy metals under micellar-enhanced ultrafiltration-based system.
Hayrynen et al. (2012) reported significant level of metal removal with least reten-
tion of phosphorous (Landaburu-Aguirre et al. 2012).
Cyanoremediation
Elevated rate of atmospheric emission of heavy metal leads to higher accumulation

in the oceanic component of the environment (Shirdam et al. 2006). As per earlier
reports, different groups of cyanophycean algae can be effectively utilized for
bioremediation in aquatic system (Deng et al. 2007; Fiset et al. 2008; Tripathi
et al. 2008; Yin et al. 2012). Recent advances include utilization of wild strain,
mutant, and genetically engineered form of cyanobacteria for decontamination
process (Yin et al. 2012). Under in vivo condition, cyanobacteria such as Syn-
echocystis sp. PCC6803 accumulate higher amount of arsenic species through
cellular oxidation mechanism (Yin et al. 2012).
Biostimulation
The potential of microbial community to use natural and synthetic substances as

energy source is a major advantageous process which can be effectively used in
bioremediation. It also helps in their colonial growth. Such efficiency can be a
suitable alternative for physicochemical methods of decontamination (Tang et al.
2007). Throughout the world, nutrient inputs to stimulate growth of indigenous
population are the most applicable form of in situ bioremediation for decontamina-
tion of contaminated site from petroleum hydrocarbon and other toxic contaminants
(Cheng et al. 2009; Tyagi et al. 2011). Biostimulation process is mediated through
application of nutrient supplements, substrate molecules for microbial growth, and
introduction of microbial strains having higher capability of degradation (Baldwin
et al. 2008).
Biomineralization
Heavy metal contamination is an inevitable consequences in an around mining area.

Research reports revealed higher level of presence of heavy metal in and around
mining areas. Migration of heavy metals from mining areas to adjacent soil and
water ecosystem is a serious threat from environment perspective. Higher presence
of heavy metal regulates the vegetation pattern of a particular site. Species develop in
the contaminated sites with metal specificity through the process of microevolution
(Ernst 2006). Metal accumulation potential is governed by availability of metal
forms in the soil along with the mineralization process. Biomineralization is the
process in which a specific form of inorganic substance is biosynthesized by
microorganisms by using the substrate molecule which may be fruitful in performing
various functions of biological system (Kim and Park 2013).
Formation of mesoporous silica nanoparticles is one such examples of biomin-
eralization process which aids in cancer therapy (Kim et al. 2010). Organic–i-
norganic hybrid molecules are synthesized through newer applications of
biomineralization technique (Achal et al. 2012b; Chen et al. 2013). Another
research reports reveal higher arsenic removal capability of Sporosarcina
ginsengisoli CR5 through biomineralization process producing enzyme urease
(Achal et al. 2012b). The inherent capability of microbes to bind metal to form
minerals are known as mineralization. The same principle can be effectively
utilized to capture heavy metal under stable solid phase. As per the scientific
study, enzyme urease promotes increment in soil pH resulting into carbonate
production. This therefore helps to mineralize heavy metal ions in the cell envelop
at pH 8–9 (Li et al. 2013). Bioremediation of lead through induced calcite precip-
itation was confirmed in South Korea by some workers (Govarthanan et al. 2013).
KK1 strain of Bacillus sp. reflected resistance against lead, and the 16S rRNA gene
sequences of the bacterium showed maximum resistance toward lead (Govarthanan
et al. 2013).
Biosorption
Radionuclides are one of the major concerns in terms of contamination of air, water,
and soil and its severe impact over human civilization. Kumar et al. (2011) reported
uranium tolerance and accumulation by Serratia marcescens strains. Molecular
analysis of the five isolates of S. marcescens reflected higher removal of uranium.
This sort of approach reveals the wider applicability of microbes toward environ-
mental cleanup of uranium. Similarly, Bacillus and Pseudomonas species are also
capable of removing uranium from uranium-contaminated site (Kumar et al. 2008b).
Studies on Pseudomonas aeruginosa J007 strain revealed 99% removal of soluble
uranium and its conversion to uranium oxide and other phosphate minerals
(Choudhary and Sar 2011). Halomonas spp. have been reported to remediate
strontium (up to 80%) through calcite precipitation from strontium-contaminated
aquifer quartz sand (Achal et al. 2012a). Such type of studies revealed the utility of
using indigenous microorganisms for removing metal radionuclides from the con-
taminated sites.
Molecular Mechanisms Involved in Bioremediation Process
Various molecular mechanisms are actively involved in metal removal by microbes.

Genetically engineered bacteria Deinococcus geothermalis reflect the gene regula-
tion activity of the mer operon of E. coli coding for protein capable of mercury
reduction (Brim et al. 2003). Recombinant DNA technology is being widely utilized
by modifying Cupriavidus metallidurans strain MSR33 which is inherently mercury
resistant. The process involves insertion of merB and merG gene through pTP6
plasmid regulating mercury biodegradation along with biosynthesis of protein mol-
ecules (Rojas et al. 2011). Pseudomonas strains were modified into mercury-
resistant form through insertions of mer novel genes (Sone et al. 2013). Two
conversion processes are actively involved in mercury biodegradation. One includes
mercury volatilization through reduction process, and the other includes precipita-
tion through conversion of insoluble mercury into volatile thiol form (Essa et al.
2002). Application of genetic engineering in the form of insertion of tod and xyl
operons through molecular cloning mechanism from Pseudomonas putida to
Deinococcus radiodurans has been reported earlier by (Brim et al. 2006).
Microbes Involved in Bioremediation
Bioremediation by Microbes
Throughout the world, contamination of air, water, and soil environment appears to be
a significant issue to mankind due to its impact as well as economic cost associated
with it. Heavy metal contamination phenomenon is strongly associated with discharge
from agriculture and industrial sectors (Ansari and Malik 2007). Within the soil
environment, heavy metal is found to be associated with free cations in soil solution
and have complex formation with organic and inorganic ligands as well as with soil
colloidal matter (Wang et al. 2010). In this way they tend to migrate in the food chain
and ultimately to the food web through diverse connectivity of food chains (Giller
et al. 1998). Soil environment comprises of diverse form of organic and inorganic
constituents such as ferromanganese, silicate clay minerals, and organic humus
materials. The nature of soil is diversified by changes in the soil pH, redox potential
value, and soil moisture regime. These in terms regulate the mobility of metals within
the soil environment (Alloway 1990). The interrelationship between soil and heavy
metal can be interpreted through diverse mechanisms of geochemical reactions.
Environmentally degraded soil poses various types of microorganisms who can
strive under polluted stress conditions; therefore, they have the ability to cope up
with the polluted condition through their own biochemical mechanism (Baker and
Banfield 2003). Various research reports revealed the nutrient recycling ability of
microorganisms which are often hindered under stress of heavy metal (Moffet et al.
2003). The mode of operation of microbes includes altered environmental conditions
through decontamination, different forms of biotransformation processes as well as
incorporation in the microbial biomass leading to lesser pollution (Bruneel et al.
2006; Hetzer et al. 2006; Guine et al. 2007). Heavy metal stress often imposes a
negative impact on microbial dynamics in soil ecosystem. It has been reported both
density and diversity reduce significantly under higher concentration of heavy metal
in soil (Wang et al. 2010).
Microbial activity in presence of heavy metal stress often appears to be a suitable
model to study the impact of toxicant on biology and physiology of microorganisms
(Guo et al. 2009). Heavy metal stress alters the physiological and biochemical
mechanism within a microbial cell leading to inhibition of attributes such as growth,
diversity, morphology, and biochemical activity (Sandaa et al. 2001; Tsai et al. 2005;
Perez-de-Mora et al. 2006). The microbial interaction with the toxicant depends
upon various important factors such as amount of heavy metal present in the
medium, heavy metal release, metal uptake capacity of microbes, as well as the
nature of the metal (Hassen et al. 1998). Elevated level of heavy metal inhibits
enzyme activity by altering its protein structure through metal replacement, compet-
itive inhibition with nonmetallic compounds within the cell, and inhibition of
functional groups of carbohydrate, protein, and fat essential for cell metabolism
(Hetzer et al. 2006). One interesting fact of survival of microbes under harsh
conditions such as heavy metal pollution depends upon the inherent genetic charac-
ter within the microbial cell as well as metal speciation in the environment (Abou-
Shanab et al. 2007). Survival of microorganism under heavy metal stress condition
reveals two modes of experiments. Short-term exposure to heavy metals helps to
identify microbes within a short span of time, but on a long-term basis, it may not be
fruitful. On the other hand, long-term exposure provides microbes to adjust them-
selves both under natural and artificial condition (Perez-de-Mora et al. 2006).
Combined effect of heavy metal is much more in comparison to sole presence of a
metal (Renella et al. 2005).
Table 2 Industrial source of metals and their utilizing microbes (fungi)

Metal Industry source Microbes References
Zinc (Zn) Smelting and Pseudomonas aeruginosa Gunasekaran
electroplating and Bacillus spp. et al. (2003)
Molybdenum Spent catalyst – –
(Mo)
Lead (Pb) E-waste, smelting Rhizopus arrhizus, Gabriel et al.
operations, and coal- Phormidium valderium, (1996)
based thermal power and Ganoderma
plants applanatum
Mercury (Hg) Thermal power plants Ganoderma applanatum Gabriel et al.
and electrical appliances and Rhizopus arrhizus (1996),
Gunasekaran
et al. (2003)
Chromium (Cr) Mining, leather tanning, – –
and industrial coolants
Arsenic (As) Smelting operations and – –
thermal power plants
Copper (Cu) Mining, smelting Bacillus spp., Gunasekaran
operations, and Pseudomonas aeruginosa, et al. (2003)
electroplating Pleurotus ostreatus
Cadmium (Cd) E-waste, zinc smelting, Aspergillus niger, Gunasekaran
and fuel combustion Pleurotus ostreatus, and et al. (2003),
Phormidium valderium Gabriel et al.
(1996)
Microbial response toward heavy metal stress can be evaluated externally through
phenotypic study as well as studying the internal mechanism at molecular level.
Several methods such as PCR, DNA hybridization, isotope study and restriction
fragment length polymorphism (RFLP), or amplified ribosomal DNA restriction
analysis (ARDRA), DNA microarray analysis, Aminoacid sequencing are some of
them (Guo et al. 2009). These advanced methods help to screen specific genes
responsible for adaptive nature of microbes (Abou-Shanab et al. 2007).
Table 2 represents a brief summary of different potential bioremediating agents
capable of removing various heavy metals from various segments of environment.
Among the various agents, Pseudomonas aeruginosa removes cadmium and zinc,
Rhizopus arrhizus and Ganoderma applanatum is capable of removing lead and
mercury, Bacillus species are capable of removing copper and zinc, and Pleurotus
ostreatus are capable of removing copper and cadmium.
Plant Growth-Promoting Bacteria (PGPB) Mediated

Decontamination of Heavy Metals
PGPB promote resistance and plant growth in plants. As a subsidiary role, they have
been reported to aid metal uptake activity in plants. Mechanisms such as
siderophore, biosurfactant and organic acid production in PGPB promote metal
uptake (Braud et al. 2009). The main process behind this is the ready translocation,
therefore reducing toxicity in root and promoting plant growth (Wu et al. 2006a).
Mostly biosorption and bioaccumulation by PGPB help in lesser uptake of metals in
plants which promotes significant level of plant growth (Jing et al. 2007).
Plant growth-promoting rhizobacteria or PGPR refer to microbial species that
inhabit in the rhizospheric zone and provide stimulation of plant growth through
diverse mechanisms (Vessey 2003). Diverse groups of microorganisms remain
present in soil rhizospheric zone and undergo various forms of interactions with
the pedosphere which promotes biological nitrogen fixation and ready release of
nutrients from soil which impact soil growth. In this way such colonization of PGPR
becomes beneficial for plants (Tank and Saraf 2009). They have also been reported
to be used in agricultural system for better crop growth and productivity (Mehboob
et al. 2011).
Metal-Microbe Interaction
Metals such as zinc, copper, cobalt, and nickel under lower concentration are very
much essential for metabolism in the bacterial cell. Pb, Cd, Hg, and Cr have no role
to play in cellular activity and are toxic for the cell (Chen et al. 2005a, b; Abou-
Shanab et al. 2007). Microbes play a key role in metal speciation and mobilization in
the various segments of the environment (Spain and Alm 2003). It was absorbed that
high concentration of heavy metals appears to be toxic for cells.
Figure 2 summarizes the various modes of metal-microbe interaction that takes
place at various segments of environment. Microbial cells have been reported to
actively participate in the processes like bioleaching, biosorption, biotransformation,
and bioaccumulation. In all these processes, microbial biomass plays active role in
heavy metal removal.
For proper understanding of metal-microbe interaction, understanding cell
structure of bacterial cell is very important. Depending upon the cell wall struc-
ture, bacteria can be classified into Gram-negative or Gram-positive. Cell wall of
Gram-negative bacteria consists of lipopolysaccharide (e.g., lipopolysaccharide
layer [LPS]), phospholipids, and a small peptidoglycan layer. On the other hand,
cell wall of Gram-positive bacteria consists of 90% peptidoglycan component
along with small amount of teichoic acid (Guine et al. 2007). Such composition
comprises of negative charge and is therefore readily adsorbed surface for metals
(Guine et al. 2007).
Bioaccumulation is a process which is specific in terms of substrate molecule
driven by ATP (Spain and Alm 2003; Errasquin and Vazquez 2003) and therefore
one of the major mechanisms for decontaminating a polluted site from heavy metal.
Passive diffusion, facilitated diffusion, and active transport are the three pathways of
metal mobilization in microbes. Among them the active transport system are very
much specific with some exceptions such as Cd transportation can be done through
the transportation of zinc. Limitation of bioaccumulation process includes structural
deterioration while metal recovery from biosorbent mass (Ansari and Malik 2007).
Microbial cells
Metal microbes
interactions
Bioleaching
Biosorption
Bioaccumulation Biomineralization
Biotransformation
Fig. 2 Bioremediation through metal-microbes interaction process
Processes regulated by the physicochemical factors such as chemiosmotic gradi-

ent without requirement of ATP are known as biosorption. Various mechanisms such
as adsorption, ion exchange, and covalent bonding can take place both in living and
dead biomass and are therefore a suitable alternative for conventional method of
metal removal from solution (Spain and Alm 2003; Chen et al. 2005a, b), which
happens to a passive system of metal uptake. The cell walls of Gram-negative and
Gram-positive bacteria are negatively charged due to the presence of carboxyl,
hydroxyl, and phosphoryl functional groups which makes them active metal-binding
sites (Marazioti 1998). Biosorption has got wider possibility in terms of its applica-
tion in bioremediation of heavy metals from wastewater (Errasquin and Vazquez
2003). Applicability of biosorption process depends upon the costing of biosorbing
material used (Chen et al. 2005a, b).
Response of bacteria toward toxic heavy metal ions reveals wider adaptability of
microorganisms to various metals (Valls and de Lorenzo 2002). Mechanisms of
wider adaptability of microbes include precipitation, complexation, adsorption,
transport, product excretion, pigments, polysaccharides, enzymes, and specific
metal-binding proteins (Marazioti 1998; Hetzer et al. 2006). Metallothioneins –
the metal-binding proteins – are a significant factor for bacterial metal tolerance
(Marazioti 1998; Valls and de Lorenzo 2002). From chemical configuration, meta-
llothioneins are cysteine-rich polypeptides which are capable of binding both essen-
tial metals (e.g., Zn) and nonessential metals (e.g., heavy metals) (Marazioti 1998).
Active efflux, complexation, reduction, and conversion of the heavy metal ions to
a lesser toxic state are some other mechanisms of microbial decontamination (Nies
1999). These are plasmid-driven processes which help in mobilization from cell to
cell (Valls and de Lorenzo 2002); chromosome resistance was also found to be
related to bacterial species (Spain and Alm 2003; Abou-Shanab et al. 2007).
Regarding bioremediation research isolation of metal-resistant bacteria such as
Cupriavidus metallidurans, CH34 reported effective bioremediation of heavy metals
from polluted soils and water. It was found that this bacterial strain is capable of
bioaccumulating selenium (Se) and gold (Au) and volatilizing Hg through reactive
processes (Reith et al. 2006). Research reports reveal isolated microbial biomass of
Pseudomonas stutzeri showed resistance toward chromium up to 1 mM and has the
capability to anaerobically reduce Cr (VI) up to 100 μM (Tsai et al. 2005).
The immense potential of microorganisms in terms of heavy metal uptake has
promoted new interest nowadays in the field of applied science to decontaminate a
contaminated environment (Valls and de Lorenzo 2002; Errasquin and Vazquez
2003). For removing heavy metal from the environment, bacteria can be a fruitful
biosorbent which further needs to be explored through proper R&D (Errasquin and
Vazquez 2003).
Gram-negative bacteria are much more resistant to Cd in comparison to Gram-
positive ones due to their complex cell wall structure (Jjemba 2004). Resistance to
specific metals may be attributed toward metallothionein proteins which are capable
of metal binding and therefore lead to detoxification. The process is associated with
effluxing Cd ions through energy-dependent mechanisms of active transport (Jjemba
2004). As per research reports, light significantly influences the adsorption capacity
of Cd of Chlorella 37 pyrenoidosa (Sirianuntapiboon and Ungkaprasatcha 2007)
which is probably applicable for some other groups of bacteria.
Metabolic activity of some microorganisms often utilizes oxidized and reduced
form of arsenic as electron acceptors. Toxicity of arsenic can be regulated by the
presence of ars gene (Oremland and Stolz 2003). Usually arsenic-resistant microbial
species were isolated from As-contaminated environment, but laboratory-scale
experiments revealed that Escherichia coli and Pseudomonas aeruginosa offer
greater resistance to high level of As contamination (Jackson et al. 2005). Phylogeny
of arsenic-resistant genes reveals their higher abundance in earlier times (Jackson
et al. 2005). This therefore indicates microbes of arsenic-free area could also have
arsenic resistance. Such microorganisms are capable of biotransforming arsenic into
less toxic condition which can be considered as an in situ remediation strategy, and
the microbial species can be used as As-resistant microbes (Jackson et al. 2005). As
oxidation by bacteria was also reported in acid mine drainage (AMD) and in hot
springs (Oremland and Stolze 2003; Bruneel et al. 2006).
A microorganism tends to maintain a balance of metal concentration within their
cell such as Zn. Microbes maintain an optimum balance between zinc requirement
and its toxicity by bioaccumulation through metabolic activity of the bacterial cell
where Zn is being detoxified (Blindauer et al. 2002). Zn can be egested out of the cell
through various exporters as well as through various uptake systems regulating Zn
uptake at diverse level of transporter synthesis and activity (Hantke 2005). Zn has
got synergistic effect in the presence of other heavy metals in aerobes and anaerobes.
However, higher level of Zn reduces protein and ATP content, undergoes interaction
with nucleic acids, inhibits enzymatic activity, and causes alteration of membrane
structure and cell death (Vega-Lopez et al. 2007).
Microbes and Metal Resistance
Gene regulation activity of bacterial plasmids often renders the cell to develop its
resistance against heavy metals (Silver and Phung 1996). Mechanism behind bacte-
rial metal tolerance process is yet to be explored properly. Some probable mecha-
nisms include active transport of metals from bacterial cell to outer environment,
interaction of metal-binding proteins, and biotransformation of metal ions to less
toxic forms (Saluja and Sharma 2014).
Plant growth-promoting bacteria (PGPB) have a stimulatory effect upon hyper-
accumulators as plant or soil inoculation under higher level of contaminant exposure
(Glick 2003). Underlying mechanism of plant growth induced by PGPB under heavy
metal stress is yet to be explored (Belimov et al. 2005).
Metal tolerance in microorganisms has evolved due to exposure of microorgan-
isms toward heavy metals after initiation of life (Girno et al. 2002). Some have
developed metal resistance due to metal exposure over the last 50 years. Nowadays
anthropogenic contributions toward environmental pollution have created the pres-
sure to explore the field microbial metal resistance and remediation. Microorganisms
happen to be the key factor toward reducing the level of contamination in the
environment. Metal resistance in microorganisms involves plasmid-encoded sys-
tems as well as general resistance toward diverse metals.
On this background, there are two mechanisms of metal resistance:
• General mechanism of metal resistance

• Metal-dependent mechanism of metal resistance
General Mechanism of Metal Resistance
Immobilization of metals through extracellular materials of cell prevents the entry of

toxic metal within the cell. Anionic cell surface actively binds metal cations such as
Pb, Cd, Zn, and Fe. Functional groups such as carboxylic, amino, thio, hydroxo, and
hydroxycarboxylic groups heavily adsorb metals. Phosphoryl groups and phospho-
lipids present in outer membrane of bacterial cell within lipopolysaccharides
undergo active interaction between them. Immobilizations of metals by microbial
cell are more important from ecological and practical point of view. In aquatic
environment, the process of cell surface binding often regulates distribution of

metals. Exploration of the capability of microbes to sorb metal has been done for
bioremediation purpose. The general mechanism of metal resistance by microorgan-
isms can be divided into four categories.
Exopolymer Binding
Extracellular polymeric substances (EPSs) such as polysaccharides, carbohydrates,
nucleic acids, and fatty acids are very much prevalent under natural condition which
provides protection to the bacterial cell as well as helps in metal binding. Microbial
exopolymers act as efficient metal binders for some metals such as Pb, Cd, and
U. Metal-binding functional groups are very much influenced by the changes in the
environmental pH due to their net negative charge. Bacterial genera such as Staph-
ylococcus aureus, Micrococcus luteus, and Azotobacter spp. have been reported to
undergo expolymer binding of heavy metals (Maier et al. 2009).
Siderophore Complexation
Siderophores are low molecular weight organic molecules capable of chelating iron
and therefore help in bioconcentrating iron into the cell. Siderophores interact with
other elements having similar chemical configuration with iron. Siderophores with
their metal-binding capacity reduce metal bioavailability and metal toxicity. Reduc-
tions of copper toxicity by siderophores have been reported in the case of
Cyanobacteria (Roane and Pepper 2000).
Biosurfactant Complexation
These are substances produced by the bacterial cell which sometimes are secreted
outside the cell. As per recent research reports, biosurfactants undergo complexation
with metals such as cadmium, lead, and zinc (Miller 1995). It has been observed that
complexed metal through biosurfactant complexation becomes less toxic to cell.
Precipitation by Metal Reduction

Bioavailability of metals can be influenced by metabolic activity within the bacterial
cell that reduces the metal molecule. Through such reduction, the solubility of metals
further decreases including sulfidic and phosphidic metal salts. Citrobacter spp. have
been reported to produce phosphates through enzymatic action which leads to
precipitation of lead and copper in the presence of oxygen. In the absence of oxygen,
Desulfovibrio spp. are reported to cause precipitation of metals (Roane and Pepper
2000).
Metal-Dependent Mechanism of Metal Resistance
Knowledge regarding intracellular metal resistance is yet to be explored properly.

Binding of metal ions by metallothioneins is most probably the best mechanism under
this category. Such mechanisms are active when metal contamination is present in the
environment. Metallothionein are very much important in terms of heavy metal
metabolism as well as heavy metal stress. Metallothionein protein molecules are
possessing higher number of cysteine residues which make them a potential detox-
ifying agent. The three specialized features of metallothioneins include low molecular
weight, cysteine-rich residue, and capability of formation of metal-thiolate clusters.
Microbial Resistance to Oxyanions
Mechanism of resistance occurs in two forms such as chromosomal or plasmid-

mediated. Plasmid resistance systems include the efflux systems. Examples include
ATPases (Cd2+ ATPase systems of Gram-positive and arsenite ATPase systems of
Gram-negative bacteria) or chemiosmotic systems such as divalent cation efflux
system of soil Alcaligenes and the arsenite efflux system of Gram-negative bacteria
as well as plasmids of Gram-positive bacteria. Microbes are capable of effluxing the
toxic metals from their cytoplasm.
Arsenic oxyanion gets entry into the bacterial cell through transporters of other
compounds. E. coli accumulates arsenate through phosphate transporters, Pit and Pst
pumps (Nies 1999; Rosen 2002). High level of phosphate promotes the Pit system to
fulfill the cell phosphate requirement which leads to accumulation of arsenate (Elvin
et al. 1987). Under lesser availability of phosphate, induction of Pst system for
phosphate uptake takes place (Surin et al. 1987). Such systems effectively utilize
PstS phosphate-binding protein and PstABC ATPase complex for uptake in the inner
membrane (Rosen 2002). In the same way in eukaryotes such as Saccharomyces
cerevisiae, eight phosphate transporters mediate the uptake of arsenate (Nies 1999;
Rosen 2002). Due to chemical similarity of arsenic and antimony oxyanions,
transportation follows the same pathway. One route of entry for Sb(III) takes place
through the glycerol facilitator, G1pF polyol transporters (Sanders et al. 1997; Rosen
2002). Effluxing is the major mechanism for most of the systems for developing
resistance for arsenite (Nies and Silver 1995; Sanders et al. 1997).
Resistance to Divalent Metal Ions
Species resistances toward heavy metals differ among microbial species. Research
reports reveal diverse mechanism of metal resistance toward divalent metals (Nies
1999). Most divalent heavy metal ions are being accumulated by unspecific CorA
(metal transport system, MIT) Mg2+ transport system (Nies 1999). Specific condi-
tion such as starvation or need induces such systems of heavy metal transport (Nies
1999).
Microbial Transformations of Metals
Microbial remediation of metal involves diverse type of processes such as catalysis,

biomethylation, accumulation, oxidation and reduction, mobilization, and formation
of biominerals. Different processes of microbial transformation of heavy metals have
been identified which help to clean the metal contamination from environment.
Microbial transformation involves metal resistance mechanisms which comprise

complexation and precipitation and solubilization of heavy metals within the con-
taminated matrix (Roane and Pepper 2000).
Mechanisms of Metal Transformation by Microbes
Biologically Catalyzed Immobilization
Metal-reducing microbial species have been reported to act on a wide array of heavy
metals. Enzymatic reduction involves utilization of metal oxides as electron accep-
tors {Cr(VI), U(VI)}. These metal oxides possess significant harm to living beings as
they are highly soluble in water leading to groundwater contamination. In these
contexts the reduced form is insoluble in nature and gets readily precipitated. Under
aerobic and anaerobic condition, hexavalent chromium can be biologically reduced.
Oscillatoria sp., Arthrobacter sp., Agrobacterium sp., Pseudomonas aeruginosa
S128, Chlamydomonas sp. (algae), Chlorella vulgaris (algae), Zoogloea ramigera,
and anaerobic sulfate-reducing bacterial species have been reported to reduce Cr
(VI) species in water contaminated with chromium (Kamaludeen et al. 2003).
Enterobacter cloacae and some other metal-reducing bacteria have been reported
to reduce chromate ion to Cr(III), which gets precipitated as Cr(OH)3 under opti-
mum conditions (Komori et al. 1989, 1990). Metal-reducing microbe acts upon
highly water-soluble uranyl carbonate (groundwater) to insoluble form of U(IV) and
precipitates as uranium oxide in mineral uraninite. Microbial binding of recent
development in this field includes conversion of biologically bound U(VI) to
U(IV) which undergoes intracellular precipitation (Lovley et al. 1993). Indirect
reductions are much more preferable in comparison to enzymatic reduction under
natural condition. Such processes are mediated by metal-reducing and sulfate-
reducing bacteria. Such processes were achieved through organic compound oxida-
tion or use of hydrogen for reducing ferric iron [Fe(III)], Mn(IV), or sulfate (SO4 2–)
(Lovley et al. 1989). Such ways lead to reduction of iron(III) to iron(II), manganese
(IV) to manganese(II), and SO4 2 to hydrogen sulfide (H2S). Such reduced species
undergo reaction with contaminants and form insoluble components. Among these
species reduced forms Fe(II) and H2S are the most active form. Utilization of Fe
(II) as an electron donor has been reported to reduce and precipitate chromium for
chromium-contaminated soil by utilizing chemical iron barrier and Fe-reducing
bacteria (Wielenga et al. 2001). Sulfate-reducing bacteria can be induced to act as
reactive redox barrier. Hydrogen sulfide-generating sulfate-reducing bacteria reduce
the contaminant directly or indirectly in sulfide minerals such as pyrite which
pretends to be stable structure for extended time period.
Biologically Catalyzed Solubilization
Microbes are directly and indirectly involved in solubilization of biosorbed and

coprecipitated metals. Such solubilization process requires partial oxidation of toxic
heavy metal present in the mineral in oxide form. Iron oxide minerals can be
dissoluted by microbial species through direct and indirect mechanisms. Bacteria
capable of reducing metals through enzymatic mechanisms can mobilize oxide
minerals under optimum environmental conditions. Anaerobe Clostridium has
been reported to mobilize cadmium, nickel, and zinc from iron oxide minerals
such as goethite through dissolution. Bacteria capable of reducing metal ion species
in the form of iron oxides have been reported to release soluble form of radium from
uranium mine tailings. Metal-reducing bacteria are also capable of mobilizing
insoluble form of heavy metals.
Aerobic
Pseudomonas, Alcaligenes, Sphingomonas, Rhodococcus, and Mycobacterium are
the few examples of few aerobes capable of biodegradability. They have reported to
have the capability of degrading pesticides and hydrocarbons such as alkanes and
polyaromatic compounds due to their effective utilization as substrate molecule for
energy production.
Anaerobic
Anaerobic bacteria are not utilized effectively as the aerobic ones. Research reports
reveal the potentiality of anaerobic systems to bioremediate polychlorinated biphe-
nyls (PCBs) from river sediments, undergo dechlorination of trichloroethylene
(TCE) and chloroform organic compounds.
Ligninolytic Fungi Such As White Rot Fungus

Phanerochaete chrysosporium effectively utilizes straw, sawdust, or corncobs as
substrate molecule to degrade diverse environmental contaminants with sufficient
persistency.
Methylotrophs
These are the aerobes that are capable of utilizing methane for carbon and energy
source. Such type of aerobic degradation process involves enzyme system such as
methane monooxygenase with wider substrate range as well as wider functionality
against various compounds such as chlorinated aliphatic trichloroethylene and
1, 2-dichloroethane (Table 3).
Microbial-Assisted Phytoremediation
The interaction between soil, heavy metals, bacteria, and plants regulates the poten-
tiality of bioremediation. Such interaction involves characteristic features of plant
and its associated microbes, climatic conditions, soil properties, etc. Soil signifi-
cantly influences the metal mobilization through changes in metal bioavailability and
exudates from root as well as nutrient level (Jing et al. 2007).
Plants significantly regulate metal concentration and metal speciation in the
contaminated environment through metal uptake and subsequent export of protons
due to uptake through antiport system which acidifies the rhizosphere and promotes
Table 3 Microorganisms involved in metal remediation

Microorganism Elements Source
Bacillus spp. Cu, Zn Gunasekaran et al. (2003)
Pseudomonas aeruginosa
Zoogloea spp. U, Cu, Ni Sar and D’Souza (2001)
Citrobacter spp. Co, Ni, Cd
Chlorella vulgaris Cd, U, Pb Gunasekaran et al. (2003)
Au, Cu, Ni, U, Pb, Hg, Zn Yan and Viraraghavan (2001)
Gunasekaran et al. (2003)
Aspergillus niger Cd, Zn Zn, Ag, Th, U Gunasekaran et al. (2003)
Pleurotus ostreatus Cd, Cu, Zn Gunasekaran et al. (2003)
Rhizopus arrhizus Ag, Hg, P Favero et al. (1991)
Cd, Pb, Ca
Stereum hirsutum Cd, Co, Cu, Ni Gunasekaran et al. (2003)
Phormidium valderium Cd, Pb Gabriel et al. (1994, 1996)
Ganoderma applanatum Cu, Hg, Pb Gabriel et al. (1994, 1996)
Volvariella volvacea Zn, Pb, Cu Gabriel et al. (1994, 1996)
metal availability under acidic condition through release of phenolics and organic
acids (Kuiters and Mulder 1993). Plant physiological process regulates trace metal
uptake from root to shoot via solution phase of soil (Violante et al. 2010). Root cells
present on the outside of the roots have a free space in which metal accumulation
takes place due to creation of a Donnan potential by the charged binding sites present
in the cell walls (Soriano-Disla et al. 2010). Plant roots can reduce metal contami-
nation and its toxic effect through ready uptake of metal ions as well as through root
features and their functions of adsorption on root or through root exudates
(Hinsinger and Courchesne 2008). Metal speciation can be changed by acidifica-
tion/alkalinization; modification of the redox potential; increasing metal/metalloid
solubility as root exudates in the form of metal chelants and organic ligands, like
mucilage, polysaccharides, and ectoenzymes; and release of compounds like carbo-
hydrates, organic acids, amino acids, peptides, phenolics, and phytosiderophores
having low molecular weight which competes for anionic species such as arsenate
toward binding sites (Wenzel 2009). Phytosiderophores are specific compounds
organic in nature which impact upon the distribution of iron and other metals
(Treeby et al. 1989). In this process the metal speciation is affected by metal
complexation by these organic acids which make lesser availability of free metal
ion concentration as well as decrease metal desorption from the solid phase of the
soil. The process having similarity with the mechanisms of organic acids is capable
of bringing protons into the rhizosphere causing lowering of the pH leading to high
free metal ion concentration (Violante et al. 2010). Utilization of plant-borne organic
compounds to improve the heavy metal removal efficiency from soil is of great
importance. Soil rhizosphere plays a very significant role in bioremediation process
due to rhizospheric interaction and rhizospheric exudates, and their proper manage-
ment leads toward success of phytostabilization and/or phytoextraction of heavy
metals in the soils. Plant-rhizobacteria interaction stimulates the production of

compounds which are capable of altering the nature of soil and its chemical
properties in the rhizospheric zone and therefore increases metal accumulation by
plant system. Metal uptake by plants leads to reduction of availability of inorganic
pollutants to microorganisms (Wenzel 2009). Microorganisms are mostly affected in
comparison to other living organisms due to their direct interaction with the envi-
ronment (Giller et al. 1999). Microbial activity has been reported to be affected by
higher metal concentrations. They have reported to play active role in metal mobi-
lization and immobilization as they are able to carry out metal biotransformation
(Turpeinen 2002). The phenomenon of microbial resistance to metals is a major
important aspect for diverse functional aspects. Microbes grow in metal-
contaminated environments which is an important aspect of microbial ecology
from pollution remedy as well as reclamation of metal-contaminated sites
(Turpeinen 2002). Different processes of microbial biotransformation such as com-
plexation, precipitation, solubilization through release of chelating agents, acidifi-
cation, phosphate solubilization, and redox changes are the outcome of microbial
mechanism of resistance (Nies 1999; Roane and Pepper 2000). Such mechanism of
transformations alters mobilization of heavy metals and its availability to plant
species which potentiates the bioremediation process (Lasat 2002; Jing et al.
2007). Biotransformation mechanisms of microbes are of two types which include
redox transformation of inorganic forms and transformation from inorganic to
organic form such as methylation and demethylation. Metal oxidation processes
are the energy provider for microbes (Tebo et al. 1997), and microbes under
reduction process in anaerobic respiration use the metal cations as terminal electron
acceptor (Jing et al. 2007). As in plant system, microorganisms produce a number of
extracellular metabolites such as polysaccharides, pigments, organic acids and
siderophores which alters metal speciation, lower pH and increases metal solubility
which makes the metal recoverable. Organic acid complexes such as citric and oxalic
acids form soluble metal complexes with reference to Fe, Al, and Zn (Strasser et al.
1994). Siderophores produced through microbes promote immobilization or mobi-
lization from charged soil minerals of metals which depends upon differential
surface charge of metal-siderophore complexes and below metal-specific pH values
(Wenzel 2009). Under phytoremediation process, soil rhizobacteria due to their
activity and high surface area-to-volume ratio provide large surface area for binding
of metals and therefore act as metal chelates (Jing et al. 2007). Microorganisms have
capability of accumulation of metals in their biomass through intracellular seques-
tration or precipitation or through metal adsorption onto cell walls (Gadd 2004) due
to exopolymer release in the surroundings immobilizing the metals. This therefore
indicates that microorganisms can work on bimodal way such as increasing solubil-
ity of metal ions leading to their higher bioavailability and toxicity on one hand and
on the other immobilizing the metal in their biomass. Such biotransformation plays
significant role in biogeochemical cycling of metals in the environment which can be
effectively utilized in bioremediation process (Lovley and Coates 1997; Gadd 2000;
Lloyd and Lovley 2001). This reflects that bacteria play a pivotal role in metal
speciation and bioavailability of heavy metals in soil (Wenzel 2009). The major
output of plant-rhizosphere microbe interaction process includes elevated level of

soil microorganisms along with their metabolic activity which promotes plant
growth in metal-polluted sites (Kamnev and van der 2000; Khan 2005).
Recent development has taken place in the field of enhancement of
phytoremediation process through active involvement of microbes (Khan 2005).
Microorganisms present in the soil play a significant role in terms of physiological
and metabolic activity contributing toward soil quality (Jing et al. 2007). Especially,
plant growth-promoting bacteria (PGPB) and, among these in particular, rhizosphere
microorganisms, termed plant growth-promoting rhizobacteria (PGPR) inhabiting
roots of plant system, promote plant growth and development under heavy metal
stress by reducing toxicity of heavy metal in plants (Jing et al. 2007). Soil microor-
ganisms are stimulated by plant root exudates comprising of organic molecules
which are used as nutrient source by microorganisms (Glick 2003). Plant growth-
promoting bacteria positively influence growth and development in various modes
such as directly and indirectly (Glick et al. 1999). Indirect promotion of plant growth
and development occurs by developing resistance against various microbial diseases
as well as from various deleterious effects of phytopathogenic organisms and
increasing overall fertility of soil contaminated by various contaminants (Zehnder
et al. 1997). Direct promotion of plant growth by PGPB was mediated through
production of compounds for steady growth of plant species as well as promoting
ready uptake of nutrients from plants (Kamnev and van der 2000). PGPB have the
capability of supplying the plant system with and fixing atmospheric nitrogen,
synthesize siderophores capable of solubilizing iron from soil and then its ready
supply to plant cells, provide protection to plants from various diseases and patho-
gens through production of antibiotic substances (Kamnev and van der 2000),
solubilize phosphorous mineralization which makes it readily available for plant
uptake (Glick et al. 1998), and promote specific enzymatic functions and biosyn-
thesis of phytohormones, decreasing level of ethylene causing alteration in the
hormonal level in the affected plant system (Glick et al. 1999; Jing et al. 2007).
Siderophore production plays an important role to ameliorate iron deficiency in
plant system under heavy metal stress. It is a known fact that plants under heavy
metal stress reflect iron deficiency which makes the plant chlorotic due to inhibition
of chlorophyll biosynthesis. As per earlier research reports, indoleacetic acid, a
phytohormone, promotes uptake of various metals by the crop system (Kamnev
and van der 2000). In this context it is important to remember that biosynthesis of
IAA is an important activity played by rhizobacterial species under plant bacterial
interaction. Any change in the biosynthetic process of rhizobacteria leads to alter-
ation in the phytostimulating capability of rhizobacteria (Khan 2005). Such pro-
cesses indicate that microbial secretion plays an important part in the
phytoremediation process of PGPB and proper understanding of the mechanisms
behind metal-microbe interaction has led to advancement in the field of soil biore-
mediation (Malik 2004). Utilization of microbial culture and their products for metal
remedy of polluted sites is an important part which is gaining importance day by day.
One such step includes bioaugmentation process which includes addition of pollu-
tion remedy species for decontamination of the polluted ecosystem thereby enhances
the metabolic capability of the species concerned. In such way it supports the genetic
diversity and variability of microbial species present in the soil which adds up the
gene pool. Such a process is very much important for enhancement of the biological
activity in mineral soil with low level of organic matter (Kamnev and van der 2000).
Bioaugmentation process facilitates the growth of plants tolerant toward environ-
mental contaminants, which exist in small amount, thereby promoting plant growth-
promoting bacteria for efficient phytoremediation of metal contaminants (Glick
2003; Violante et al. 2010).
Designer Microbes Approach
One of the major steps ahead in the field of bioremediation is the formulation of
genetically engineered microorganisms (GEM) in which the genomic structure of the
microbial species is being altered through rDNA technology for target-oriented
cleanup process of contaminant present in soil, water, and activated sludge. Such
approach also promotes cleanup contaminants of wider dimension (Sayler and Ripp
2000). Another major advantage of such type of approach includes applicability
under environmental stress condition. Genetically engineered microbes are capable
of withstanding environmental stress condition with enhanced level of bioremedia-
tion activity.
Rhizosphere Engineering
Engineered bioremediation strategies involve either the addition of growth stimula-

tors (electron acceptors/donors) to the rhizosphere for reduction of heavy metals or
addition of nutrients to the contaminated soil for enhancement of microbial growth
and bioremediation properties of microorganisms or genetically modified plants
(Lovley 2003). Many engineered bacteria with heavy metal reduction capacity
through the expression of improved enzymes like chromate and uranyl reductase
were applied in a specific rhizosphere to perform a specific function. Similarly,
genetically modified plants are also known to produce specific compounds which
may support the rhizospheric transformation of heavy metals. Recently, several
researchers have applied these approaches to remediate heavy metal-contaminated
soils using the rhizosphere ecosystem.
Manipulation of Plant-Microbe Symbiosis
The main drawbacks of phytoremediation technology are storage and accumulation

of pollutants in the plant materials and the remediation process slowing down and
often becoming inadequate when the contaminated site has multiple pollutants
(Ma et al. 2011). The appropriate solution to these problems is to combine the
microbe-plant symbiosis within the plant rhizosphere (Wu et al. 2006) or to
introduce microbes as endophytes to allow degradation of pollutants within the plant

tissues (Van Aken et al. 2011). The microbial population in the rhizosphere is much
higher than present in vegetation-less soil, and this is due to the facilitation provided
by the plants through release of substances that are nutrients for microorganisms.
This approach has been evaluated under laboratory conditions, and if it succeeds in
field conditions, this technology could facilitate accelerated removal of pollutants,
which in turn will support high plant biomass production for bioenergy. The major
strategies for implementing bioremediation processes include biostimulation and
bioaugmentation approaches guided by specific microbes in combination with
plants. Biostimulation involves adding supplements to a contaminated site with the
objective of stimulating growth of the microbial population already present there,
which may be capable of degrading the contaminants. Bioaugmentation refers to
addition of selected and acclimated microbial inoculation to the environment that
does not contain microbes capable of degrading the contaminants.
Future Prospects: Microbial Remediation and Its Application
Gradual development of science and technology has produced numerous drawbacks

in terms of land degradation and impairment in soil quality. A conventional method
of decontaminating environment is associated with significant level of complexities
which have promoted microbes to be used as a bioremediating agent. But bioreme-
diation has its own inherent problems: certain species are incapable of breaking
down toxic contaminants into harmless condition, and these species also inhibit
other microbial activities. Alteration in the outer membrane protein of bacteria
improves the metal-binding capacity which subsequently improves the biotransfor-
mation of toxic metals. Aiming toward improving in situ bioremediation strategies
involves future outlook to explore the potential of GEM and their applicability under
multiple stress condition. Applicability of GEM under field condition is a major
challenge due to its acceptability among common public as well as it depends upon
their nontoxic nature.
Micro-remediation is a process in which microorganisms are promoted to decon-
taminate various environmental pollutants and toxicants from different segments of
environment as well as from various waste materials. Such activities of microbial
organisms are very much effective in soil environment. Bioaccumulation and
biosorption are the two active and passive mode of action of microbes for
decontamination.
Irma et al. (2013) reported the potential role of Aspergillus fumigatus fungal
isolate for active biosorption of heavy metals. Fungal isolates from compost revealed
effective detoxification of diverse metal pollutants (Vargas et al. 2009). Addition of
organic amendments such as biosolids, MSW, and compost in the soil has revealed
improved bioavailability of metals to microbes for its effective reduction of concen-
tration from soil environment (Jin et al. 2011). Hadis et al. (2011) explored
arsenite-resistant bacteria and arsenite-resistant isolates for arsenite removal from

the environment. B. macerans reported 92% removal efficiency along with
bioaccumulation potential.
Narayanan and Natrajan (2011) reported the bioremediation efficiency of
Thiobacillus spp. and Pseudomonas spp. in case of effluents released from magna
site and bauxite mines. P. aeruginosa were found to be most effective than
T. ferrooxidans in terms of reduction/absorption of heavy metals. Both the species
were found to be effective in absorbing Cd, Ca, and Zn followed by Pb. Muhammad
et al. (2007) reported a research report about the effectiveness of loofa sponge-
immobilized fungal biomass toward removal of lead ions from aqueous solution. As
per the research report, white rot basidiomycete Phanerochaete chrysosporium
along with readily available loofa sponge reflected higher removal of Pb (II) very
effectively from solution. Loofa sponge-immobilized fungal biomass reflected a
higher uptake (24.27%) over free fungal biomass (FFB).
Loofa sponge-immobilized fungal biomass was regenerated through HCl acid
treatment 99% recovery of functionality of lead removal and therefore reused for
seven times with no such lesser biosorption potential. FBILS were found to have a
very much stable structure with least interference of pH, temperature, and agitation
with no visible change in shape, structure or texture, pH, temperature, and agitation.
Conclusion
Bioremediation happens to a suitable alternative in the future in comparison to other

physicochemical processes of decontamination as a cost-effective eco-friendly tech-
nology. The process of bioremediation is influenced by various biotic and abiotic
factors. Bioremediation process is used to decontaminate the contaminated site
through various mechanisms such as adsorption, uptake, or accumulation by
microbes. The effectiveness of bioremediation process involves use of indigenous
microorganisms strategically to achieve successful level of decontamination. As an
eco-friendly approach, bioremediation technology has been proved to be very much
effective under field condition.
Sustainable management practice includes application of beneficial bacteria to
promote plant growth and reduce heavy metal contamination. Gradual understand-
ing of biological interaction within the rhizosphere would facilitate contemporary
progress in our understanding of the biological interactions that occur in the rhizo-
sphere which could facilitate PGPR growth and development leading to its wider
applicability. In terms of further research, multifactor heavy metal stress (such as Zn
and Ni) under legume and nonlegume-based systems along with PGPR presence and
rhizobial interaction needs to be judged properly. Land is often associated with
multifactor stress; therefore, multiple interactions of various stress factors need to
be properly addressed as major thrust area of research. In spite of being advanta-
geous over phyto- and bioremediation, microbial remediation happens to be least
effective due to higher level of toxicity of chemical toxicants making its use limited.
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Biostimulation and Bioaugmentation:
An Alternative Strategy for Bioremediation 20
of Ground Water Contaminated Mixed
Landfill Leachate and Sea Water in Low
Income ASEAN Countries
Jubhar C. Mangimbulude and Ronald Kondo Lembang
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516
Landfill Leachate–Contaminated Groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 517
Intrusion of Seawater into Contaminated Groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
Groundwater Management Strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
Bioremediation as a Technology for Contaminated Groundwater Remediation . . . . . . . . . . . . . . . 520
Principles of Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 520
On-Site Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524
Bioaugmentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524
Determining Potential Microbes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
Biostimulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
Factors to Consider . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 530
Abstract
The occurrence of groundwater pollution in some parts of Association of South-
east Asian Nations (ASEAN) countries has been studied in the last two decades,
and it has been found that the groundwater in these regions is in a critical state
owing to contamination. Owing to financial constraints and a lack of available
land, coastal areas and salt marshes, which generally have relatively little direct
economic value, are often converted into waste disposal sites. Many landfills are
not properly constructed. Consequently, leachate flows may contaminate the
groundwater. Landfill leachate contains complex pollutants, which can lead to
difficulties in groundwater remediation. In some cases, it was found that ground-
water had been contaminated by a landfill leachate–seawater mix. Numerous
J. C. Mangimbulude (*) · R. K. Lembang

Faculty of Natural Science and Engineering Technology, University of Halmahera, Tobelo, North
Mollucas, Indonesia
e-mail: christianjubhar@yahoo.com; klronald4@gmail.com

https://doi.org/10.1007/978-3-319-73645-7_13
516 J. C. Mangimbulude and R. K. Lembang
studies have reported that the remediation of contaminated groundwater could be

carried out on site in several ways, such as augmentation and biostimulation.
Conceptually, both strategies could be applied and widely accepted as remedia-
tion technologies. A proper understanding of bioaugmentation and biostimulation
protocols is key. Added nutrients and specific compounds such as osmolytes are
required to protect microbes from osmotic stress. Some researchers have reported
that various low-molecular-weight organic compounds such as amino acids,
quaternary ammonium, and glycine betaine could function as osmoregulatory
compounds. Screening of microbes for augmentation and monitoring the fate of a
microbial community during such processes are very important and can be done
using laboratory assays (microcosm study) and by targeting functional genes or
other molecular microbial techniques.
Keywords
Bioaugmentation · Biostimulation bioremediation · Leachate · Osmolyte ·
Functional gene
Introduction
More than two billion people in low- and lower-middle-income Association of

Southeast Asian Nations (ASEAN) countries depend on groundwater for daily
needs such as drinking water supply, agriculture, and industry. Thus, groundwater
is an essential source of freshwater for economic, social, and environmental benefits.
However, because of environmental degradation, urbanization, rapid expansion, and
exploitation may pose several problems, such as human health risks and clean water
resource availability (Ha et al. 2014).
The occurrence of groundwater pollution in some parts of ASEAN countries has
been studied over the last two decades, and groundwater in these regions has been
found to be in a critical state owing to contamination (Shivakoti 1998; Hara 2006;
Abbaspour 2011). In general, sources of groundwater contamination can be grouped
into two main categories: (a) naturally occurring pollutants and (b) anthropogenic
pollutants. Natural occurring pollutants refer to the alteration and deposits of elements,
including salts, arsenic, fluoride, chromium, and cadmium, that exceed international
or national standards for drinking water (USEPA 2006). For instance, it has been
reported that groundwater in some parts of Bangladesh, Vietnam, Pakistan, Nepal,
India, Vietnam, and Thailand contains arsenic and fluorine (Hara 2006; Islam et al.
2004; Jindal and Ratanamalaya 2003). Further, more than 35 million people in
Bangladesh consumed drinking water from groundwater contaminated with arsenic
(Islam et al. 2004). Arsenic occurs naturally in sedimentary and volcanic rocks and is
often found in sulfide forms such as realgar (Selvin et al. 2002). In addition, arsenic is
present in the crystalline structure of many sulfide minerals as a substitute for sulfur
(Smedley and Kinniburgh 2002). On the other hand, seawater intrusion into ground-
water is a source of natural occurring pollutants. Tole (1997) reported that coastal
groundwater resources are in very critical danger of contamination by seawater. Rapid
20 Biostimulation and Bioaugmentation: An Alternative Strategy for. . . 517
extraction of groundwater near shorelines will cause groundwater levels to drop and
allows seawater to flow into groundwater. The rise of seawater levels and natural
disasters like tsunamis may increase the occurrence of seawater intrusion (Kontar
2007). Anthropogenic pollutants refer to waste from human activities in agriculture,
industry, and urban areas. Such waste (residual) contains hazardous compounds and
may affect the quality of groundwater resources (Hossain et al. 2014).
Because of financial constraints and a lack of available land, coastal areas and salt
marshes, which generally have relatively little direct economic value, are often
converted to waste disposal sites (Hoornweg et al. 1999). In many Third World
countries, landfills are been located in coastal areas, where they can become polluted
(Khoury et al. 2000; Olobaniyi and Owoyemi 2006). For instance, groundwater
surrounding the Keputih landfills in Surabaya-Indonesia was contaminated by leachate
and affected by seawater intrusion (Rachmansyah 2001; Mangimbulude et al. 2016).
This chapter discusses the occurrence of groundwater pollution caused by landfill
leachate–seawater mixtures in coastal areas in some parts of low- and lower-middle-
income ASEAN countries and considers an alternative strategy for bioremediation.
Landfill Leachate–Contaminated Groundwater
Final waste disposal is a part of urban waste management, which is widely practiced
around the world, especially in developing countries, because it is cheap and easy to
do. However, in many cases, final disposal can be a threat to groundwater resources
if not properly designed and managed. Visvanathan et al. (2005) reported that more
than 90% of all landfills in South and Southeast Asia are nonengineered disposal
facilities. This creates considerable health, safety, and environmental problems such
as soil and aquifer pollution (UNEP 2004; Chofqi et al. 2004). Hence, in many cases
groundwater-related problems in coastal areas of some parts of Southeast Asia are
due to unregulated final waste disposal (landfill). This leads to landfills becoming
contaminated with a dark-brown liquid called leachate. It is generated as a conse-
quence of water contact with solid waste and due to decomposition processes of
solid wastes in landfills. Leachate may percolate into the soil and eventually reach
groundwater. Generally, leachate contains a variety of chemical substances
(dissolved organic matter, inorganic compounds, heavy metals, and XOC com-
pounds). To date, more than 1000 organic chemicals have been identified in ground-
water contaminated by landfill leachate (Christensen et al. 2001). Those chemicals
can be categorized into four groups: (a) aromatic hydrocarbons, (b) halogenated
hydrocarbons, (c) phenols, and (d) pesticides. Table 1 shows the organic chemicals
observed in groundwater. A detailed discussion of organic compounds in ground-
water contaminated by landfill leachate can be found in Cozzarelli et al. (2000),
Christensen et al. (1994a, 1994b, 2001), Bjerg et al. (2003), and Li et al. (2015).
A simple parameter often used to determine the presence of organic matter in
contaminated groundwater is biochemical oxygen demand (BOD) or chemical
oxygen demand (COD). By definition BOD is refers to the amount of oxygen
required by microbes to break down the organic matter in a water of sample, while
Table 1 Observed Compounds

selected organic pollutants
Aromatic hydrocarbon
in contaminated
groundwater Benzene
Toluene
Ethylbenzene
Xylene
Naphthalene
Halogenated hydrocarbon
Chlorobenzene
Tetrachloroethylene
Chloroethane
Chloroform
1,1-Dichloroethane
1,1,1-Trichloroethane
Trichloroethylene
Phenols
Phenol
Cresol
Chlorophenol
Penta chlorophenol
Nitrophenol
Pesticides
2-Hydroxybiphenyl
Benzamide
Furan
Atrazine
Source: Christensen et al. (2001) and Bjerg et al. (2003)
COD is refers to the amount of oxygen required by chemical (Potassium dicromate)

to oxidize organic matter present in sample of water (Tchobanoglous and Burton
1991; APHA 1998). A BOD value of 1 mg/L indicates the presence of oxidizable
contaminants or water status of high quality. On the other hand, high BOD values
(5–10 mg/L) indicate the presence high amounts of organic contaminants or a water
status of low quality (Kim 2005). The COD value also indicates the presence of
organic contaminants. A COD value of groundwater greater than 7.5 mg/L is
considered to indicate water of poor quality (Esa 1983).
Intrusion of Seawater into Contaminated Groundwater
A groundwater-related problem in coastal areas of some parts of ASEAN countries is

the intrusion of seawater. Nevertheless, the main groundwater issue in coastal area
basically has to do with landfill leachate and seawater intrusion simultaneously.
Table 2 Categories of SR value Category

groundwater contaminated
(<0.5) Good quality
due to seawater intrusion
(0.5–1.3) Slightly contaminated
(1.3–2.8) Moderately contaminated
(2.8–6.6) Injuriously contaminated
(6.6–15.5) Highly contaminated
As mentioned, landfill leachate–contaminated groundwater is indicated by the pres-

ence of organic compounds and contamination by seawater intrusion is indicated by
elevated levels of concentration of several major ions such as Cl, Na+, and SO42
(Ekhmaj et al. 2014; El Moujabber et al. 2006). A commonly used parameter to
determine the occurrence of seawater intrusion is the Simpson ratio (SR) as
described by Todd (1959). This ratio can be calculated using the following equation:

SR ¼ ðCl Þ= HCO3 CO3 2 : (1)
Todd (1959) suggested, based on Eq. 1., that contamination of water due to
seawater intrusion can be classified into five categories (Table 2).
Lee and Song (2007) reported that, besides the Simpson ratio, another ratio that
includes HCO3/Cl, Na/Ca, Ca/Cl, Mg/Cl, and Ca/SO4 would be useful to determine
seawater intrusion, which they demonstrated when they studied the implications of
seawater intrusion on groundwater chemistry in a western coastal aquifer of Buan,
Korea.
The occurrence of seawater intrusion into groundwater contaminated by landfill
leachate using SR values remains critical. It is hard to distinguish between present
saline water from seawater and contaminated groundwater-landfill leachate. How-
ever, this chapter does not discuss which is the proper method to use to determine the
occurrence of seawater intrusion. The important thing to consider is that seawater
intrusion may influence temporal hydrochemistry processes and may result in
elevated saline groundwater.
Groundwater Management Strategies
Landfills produce leachate over long periods, even 30 years postclosure (Kjeldsen
et al. 2002).Therefore, organic compounds from landfill leachate are persistent
in groundwater, while groundwater in coastal areas is vulnerable to becoming
mixed with seawater owing to intrusion. Groundwater contaminated by a landfill
leachate–seawater mixture undergoes more complex hydrochemical processes.
This condition creates difficulties for remediation.
The critical issue of groundwater contaminated by landfill leachate–seawater
mixture in coastal areas of ASEAN countries has received serious attention from
governments in the past decade. This could explain the implementation of several
strategic policies and regulations in connection with groundwater resources so as to

protect groundwater and even remediate contaminated groundwater (WEPA 2012).
Groundwater quality management therefore involves the maintenance of the fitness
for use of water resources on a sustained basis by achieving a balance between
socioeconomic development and environmental protection (Abbaspour 2011).
A basic question in this connection concerns the proper technology to use in
low-income ASEAN countries. This and other questions will be discussed in the
following sections.
Bioremediation as a Technology for Contaminated Groundwater

Remediation
Cleaning up contaminated groundwater is part of groundwater management and

policy in order to provide sustainable clean water for human activities. The National
Research Council (2000) has reviewed engineered systems like a conventional pump
and treatment system for groundwater restoration at 77 sites and concluded that
engineered systems show promise but remain unproven for the wide range of
contaminants and geologic settings of concern. Pumps and treatment systems for
groundwater restoration have been used in the USA and Europe. This method is
resource intensive and expensive. In the context of low- and lower-middle-income
countries with limited skilled human resources and financial constraints, low-cost,
effective technology is required.
Nowadays, bioremediation is used widely as a technology and strategy for
environmental remediation. By definition, bioremediation is the use of living organ-
isms, primarily microorganisms (microbes), to degrade environmental contaminants
into less toxic forms (Mary Kenza 2011). According to EPA (2013), bioremediation
is an engineered technology that modifies environmental conditions (physical,
chemical, biochemical, microbiological) to encourage microorganisms to destroy
or detoxify organic and inorganic contaminants in the environment. Many studies
have reported on the use of bioremediation at a number of sites worldwide, including
Europe and the USA, with varying degrees of success (Sims et al. 1992; EPA 2013;
Alvares and Illman 2005). Some researchers assert that bioremediation is effective at
restoring polluted environments in an eco-friendly way and at very low cost
(Thompson et al. 2005; M’rassi et al. 2015; Stroo 2010; Azubuike et al. 2016).
Referring to the foregoing definitions, it is clear that microorganisms are key players
in all steps of bioremediation. A better understanding of how microorganisms
function is required for a proper implementation of protocols.
Principles of Bioremediation
Microbes (archaea and bacteria) are unicellular microscopic organisms, as varied

and diverse as the kinds of environments on Earth (Capelle 1993). In nature,
microbial populations interact with other species’ populations as a microbial
Electron
acceptors
pH CO2
Carbon,
Nitrogen Microbes Products
Sources
Temperatura
electron H2O
donors
Fig. 1 Illustration of nutrient requirement of microbes. Microbes require carbon, nitrogen, and
energy and are supported by favorable conditions such as pH and temperature for their growth and
metabolism. Microbes are able to use various organic compounds including groundwater contam-
inants as carbon and energy sources and can grow in varied environmental conditions
Table 3 Types of microbes based on energy, carbon, and electron sources

Nutrient Source Type of microbe
Energy Light Phototroph
Chemicals Chemotroph
Carbon Organic compound Heterotroph
Inorganic compound Autotroph
Electron donors Organic compound Organotroph
Inorganic compound Litotroph
Table 4 Groups of microbes based on nutritional requirement

Energy source Electron donor Carbon source Name
Sunlight Organic Organic Photoorganoheterotroph
Inorganic Photolorganoautotroph
Inorganic Organic Photolitoheterotroph
Inorganic Photolitoautotroph
Chemical compounds Organic Organic Chemoorganoheterotroph
Inorganic Chemoorganoautotroph
Inorganic Organic Chemolitohetertroph
Inorganic Chemolitoautotroph
community. The diversity and abundance of microbes in a microbial community are

affected by several resources (carbon, energy, and nitrogen), electron donor/accep-
tor, and environmental conditions (e.g., temperature, pH) that prevail in their habitat
(Brock 2012). In other words, all microbes require sufficient resources and suitable
conditions for their growth and metabolism, as illustrated in Fig. 1. Generally,
microbes can be classified based on their nutritional requirements (Tables 3 and 4).
The types of microbes used for remediation are well known based on the nutrients
present at contaminated sites.
The literature describes in detail the fate of organic compounds in nature, which
depends on the availability of electron acceptors (Baun et al. 2003; Christensen et al.
2001; Cozzarelli 2001). Thus, the presence of electron acceptors in contaminated
groundwater indicates the potential of microbial transformation. The state and fate of
contaminants in all environments are highly dependent on the redox or valence state
of the environment. The redox potential of the environment will control the direction
of chemical balance and whether the contaminant is reduced or oxidized (Baker and
Herson 1990).
Microbial degradation of organic compounds in contaminated groundwater
occurs under different redox zones. When microbial degradation involves the use
of oxygen as electron acceptor, it is called an aerobic process, and when it uses other
electron acceptors instead of oxygen (such as nitrate, manganese, iron III, and
sulfate), it is called an anaerobic process. If all electron acceptors are present, oxygen
will be used first, followed by nitrate, manganese, iron, and sulfate. Finally,
methanogenesis and fermentation reactions dominate when the most favorable
electron acceptors are depleted (Christensen et al. 2001; Bjerg et al. 2003). Sequence
redox zones is illustrated in Fig. 2. Christensen et al. (2001) and Bjerg et al. (2003)
explain in detailed that in aquifers with continuous leachate (contaminant source)
release, a methanogenic zone is close to the source. Within this zone and down
gradient of it, sulfate reduction may take place. Iron reduction takes place further
down the gradient where conditions become less sulfate reducing. Manganese and
nitrate reduction zones have been observed to sometimes overlap with the iron
reduction zone. Aerobic conditions may exist on the outskirts of a reduced plume
if a pristine aquifer is oxidized and contains significant amounts of dissolved oxygen
(>1 mg/L). A similar illustration of redox zones was also reported by Lovely (2003),
that is, there are distinct zones in which different degradation processes predominate.
At the source of contamination, such as the leachate from landfill, methane produc-
tion often predominates. In this zone, microbes convert organic contaminants into
simpler molecules, such as acetate and hydrogen. In other zones, organic contami-
nants are oxidized to carbon dioxide with the reduction of sulfate, iron (III), nitrate,
or oxygen. Generally, the degradation of organic contaminants takes place in
different redox zones, but chlorinated contaminants, which are not easily oxidized,
undergo reductive dechlorination in methanogenic, sulfate-reduction, and iron (III)-
reduction zones (Lovely 2003).
Generally, microbes gain energy for growth through substrate breakdown. How-
ever, in some cases, under mixed substrates, some microbe communities are able to
degrade a certain substrate partly or completely, but not in support of growth. In such
conditions this is called cometabolism. According to Dalton and Stirling (1982),
cometabolism is the transformation of a nongrowth substrate in the obligatory
presence of a growth substrate or another transformable compound. The term
“nongrowth substrate” describes compounds that are unable to support cell replica-
tion as opposed to an increase in biomass. This definition was devised primarily as a
result of nongrowth substrate metabolism studies with methane-utilizing bacteria.
Janke and Fritsche (1985) reviewed the significance of microbial cometabolism, and
they explained that microbial cometabolism of xenobiotics in natural ecosystems
occurs at slow rates and will not increase in number or biomass. However, they
Flow line
Manganese red.
Methanogenic
Denitrification
Sulfate red.
Iron red.
Aerobic
oxidized sp.
SO42– O2
Dissolved
NO3–
oxidized sp.
Solid
Fe(III)
Mn(IV)
Fe(II)
reduced sp.
Dissolved
DOC
Mn(II)
S(–II)
reduced sp.
Solid
Fe(II)
S(–I,–II) Mn(II)
Fig. 2 Schematic redox zonation in an originally aerobic aquifer down-gradient from landfill, and
distribution of redox species along a streamline (axes not to scale) (Source: Christensen et al. 2001;
Bjerg et al. 2003)
concluded that under high concentrations of biomass and appropriate substrate

mixtures, cometabolism of synthetic chemicals may be a useful technique of con-
siderable practical importance to accumulate biochemical products at high yields. In
addition, the cometabolic capabilities of wild-type microorganisms may serve as a
tool for the construction of microbial strains with a new degradative potential for
recalcitrant xenobiotic compounds. Since the microbes do not rely on pollutants for
growth, the cometabolic degradation of environmental pollutants has the potential to
achieve biodegradation goals.
The presence of microbes with the appropriate metabolic capabilities is the most
important requirement in bioremediation. Thus, analysis and selected desired
microbes as a biological engine for remediation may be recommended as parts of
a bioremediation procedure. The microbes may be indigenous to a contaminated area
or they may be brought in from other habitats into the contaminated sites.
AN understanding of the correlation between microbes and their nutrients in
nature is an important step toward developing an innovative, strategic approach to
bioremediation technology. It should be noted that, individually, microbes cannot
mineralize most hazardous compounds completely. Complete mineralization results
in a sequential degradation by a consortium of microbes and involves synergism and
cometabolism actions. Natural communities of microorganisms in various habitats
have an amazing physiological versatility; they are able to metabolize and often
mineralize an enormous number of organic molecules (Singh et al. 2014).
Overall, the essential point of bioremediation is how to optimize all environmen-
tal conditions and sufficient nutrients (including electron acceptors) to support the
biological function of microbes in breaking down contaminants.
On-Site Bioremediation
Successful bioremediation technology in practice is strongly correlated with the user’s

(practitioner’s) understanding of the principles of bioremediation. In the context of low-
and lower-middle-income ASEAN countries with financial constraints and a lack of
available land, it would be wise to use an appropriate technology and strategy. Among
existing bioremediation strategies, on-site bioremediation is the right choice. On-site
bioremediation refers to a bioremediation process that takes place directly on the site of
contamination. Many studies have shown that on-site bioremediation is economical
because it does not involve the removal of contaminated groundwater to the surface
(Mary Kenza 2001; Baker and Herson 1990), so it significantly reduces operating costs
and exposure risk for personnel.
Innovations aimed at enhancing bioremediation processes could be made with
reference to the principles of bioremediation. Currently, bioaugmentation and
biostimulation have been applied to improve the rates of contaminant biodegradation
in contaminated sites.
Bioaugmentation
The rate of biodegradation of contaminants in groundwater depends on the concen-

tration of the contaminants and the amount of microbes present. The concentrations
of contaminants and microbes often change over time. When the amount of microbes
is low, the addition of microbial cultures to the contaminated sites is required to

enhance biodegradation rates; this is called bioaugmentation. The issue is what type
of microbes to add. The microbes that are used should have the capability to
grow and degrade the existing contaminants. Commonly, indigenous or microbe
communities from other environments are used. Generally, microbes identified as
active members of microbial consortiums include Acinethobacter, Actino-
bacter, Acaligenes, Arthrobacter, Bacillins, Berijerinckia, Flavobacterium, Methy-
losinus, Mycrobacterium, Mycococcus, Nitrosomonas, Nocardia, Penicillium,
Phanerochaete, Pseudomonas, Rhizoctomia, Serratio, Trametes, and Xanthofacter
(Singh et al. 2014). Adebusoye et al. (2007) have found nine microbial strains that
degraded petroleum hydrocarbons in a polluted tropical stream in Lagos, Nigeria.
Those strains are Pseudomonas fluorescens, P. aeruginosa, Bacillus subtilis, Bacil-
lus spp., Alcaligenes sp., Acinetobacter lwoffii, Flavobacterium spp., Micrococcus
roseus, and Corynebacterium spp. Wenderoth et al. (2003) demonstrated in micro-
cosm experiments the effectiveness of adding aerobic chlorobenzene-degrading
bacteria (Pseudomonas putida GJ31, Pseudomonas aeruginosa RHO1, Pseudomo-
nas putida F1DCC) to groundwater contaminated with chlorobenzene, which stim-
ulated chlorobenzene depletion.
In cases of groundwater contaminated by landfill leachate–seawater mixtures,
microbial communities with specific capabilities for degrading contaminants and for
growing in high-osmotic-pressure or high-saline environments must be used. Halo-
philic microbes are very important in the bioremediation of organic contaminants in
coastal groundwater contaminated with seawater. For instance, Karajić et al. (2010)
reported that halotolerant microbes are able to decrease organic compounds in saline
wastewater treatment. Moreover, in a recent study, Bonete et al.(2015) reported that
haloarchaea (salt-loving organisms) that can grow in media with high salt concen-
trations in a range of 12–30% salt (2–5 M NaCl) are good biological agents for
bioremediation in water treatment processes and in saline and hypersaline environ-
ments contaminated with toxic compounds such as nitrate, nitrite, ammonia, chlorine
compounds such as perchlorate and chlorate, hydrocarbons, and heavy metals. New
advances in the understanding of haloarchaea metabolism, biochemistry, and molec-
ular biology suggest that general biochemical pathways related to nitrogen (nitrogen
cycle), metals (iron, mercury), hydrocarbons, or phenols can be used in
bioremediation.
Determining Potential Microbes
Laboratory assays of potential microbes from site samples are an important step in
the evaluation of the efficacy of a process. The assay, which measures microbial
activity in a microcosm, should be done as soon as possible after taking site samples.
However, determination of the potential for contaminant degradation requires long
incubation times (in itself a disadvantage) and thus might be affected by post-
sampling changes (Röling and van Verseveld 2002). In some cases, differences in
results measuring microbial potential obtained by laboratory assays (microcosms)
and in the field were found. For instance, Smith et al. (2005) showed in laboratory
assays that the bacterial strain PM1 rapidly and completely biodegraded MTBE in
groundwater sediments. The bacterial culture was injected in an in situ field study at
Port Hueneme Naval Construction Battalion Center in Oxnard, California. Six
months after treatment began, MTBE concentrations in monitoring wells down-
gradient from the injection bed decreased substantially in the shallow zone of the
groundwater.
In recent years, advances in technology in molecular microbial and analytical
chemistry have been developed together, making it possible to identify in situ
microbial population structures, and even individual cells, responsible for triggering
specific processes (Lovely 2003; Thompson et al. 2005). Molecular techniques, such
as denaturing/temperature gradient gel electrophoresis (D/TGGE), terminal restric-
tion fragment length polymorphism (tRFLP), and polymerase chain reaction (PCR),
are better approaches to obtain a more comprehensive assessment of the composition
and structure of microbial communities in contaminated sites (Watanebe and Baker
2000; Röling and van Verseveld 2003; Lovely 2003).
An important question is how to analyze the functions (physiological features) of
microbial populations detected by molecular ecological methods. Several molecular
methods for analyzing the in situ functions of microbial populations have been
developed. For instance, metabolically active members of microbial consortia can
be identified by quantifying rRNA molecules of different species, since the ribosome
content of microbe cells is linearly related to growth rate (Watanabe and Baker
2000). Specific information on the potential for bioremediation of a certain contam-
inant can be obtained by assessing the functional genes that are responsible for its
degradation (Brockman 1995; Stapleton et al. 1998).
Specific functional targeting genes (catabolic gene) can be amplified by PCR
from environmental DNA samples and sequenced to analyze the composition and
diversity of catabolic populations. For instance, Staat et al. (2011) applied targeting
functional genes encoding specific enzymes, benzylsuccinate synthase a-subunit
(bssA) and 6-oxocyclohex-1-ene-1-carbonyl CoA hydrolase (bamA), to determine
the presence of mono-aromatic-degrading bacteria in groundwater contaminated by
landfill leachate. DNA extracts from contaminated sites were amplified by PCR
using specific primers for bamA and bssA genes. The positive results from the PCR
products indicated the presence of those microbes at the contaminated sites. The
same approaches can be used for other targeting functional genes. Recently, func-
tional genes encoding osmolyte synthesis (Mpgsmt and Mpsdmt genes) have been
amplified by PCR and can be used as probes for characterizing the presence of
osmotolerant microbes in sites (Lai and Lai 2011).
The most important question in bioaugmentation is this: How do we monitor the
fate of introduced microbes and their interactions within indigenous communities?
To monitor the fate of introduced strains, fluorescence in situ hybridization (FISH) is
used. To detect the structure and dynamics of indigenous communities during
degradation experiments, single-strand conformation polymorphism (SSCP) analy-
sis of 16S rDNA has been used (Schwieger and Tebbe 1998). Detailed explanations
of molecular microbial techniques for bioremediation have been reviewed by

Widada et al. (2002), Röling and van Verseveld (2002), Wenderoth et al. (2003),
and Lovely (2003).
The study of microcosms (culture-dependent method) and molecular microbial
techniques (culture-independent method) are complementary to each other and are
still used to assess the microbial potential in environments.
Biostimulation
Biodegradation of contaminants in soil/groundwater can be affected by certain

factors, including nutrient pH, temperature, electron acceptors, growth supplements,
and contaminant concentrations. Biostimulation is defined as optimizing all envi-
ronmental conditions such as by addition nutrients, electron acceptors, and essential
growth factors and by controlling the pH/temperature to stimulates microbial activ-
ities (Margesin and Schinner 2001; Perfumo et al. 2007; Adams et al. 2015).
Biostimulation is dependent on the indigenous organisms and thus requires that
they be present and that the environment be capable of being altered in a way
that will have the desired bioremediation effect (Hazen 2010). Studies have
shown that nutrients (nitrogen, phosphate, or carbon in the form of molasses) are
needed for microbial cell growth (Hazen 2010; Adam et al. 2015). Generally, the
levels of nutrients (nitrogen and phosphate) are proportional to the presence of
carbon (contaminants). The general theoretically calculated ratio of C:N:P for the
biodegradation of polycyclic aromatic hydrocarbon (PAH) compounds is 100:10:1
(expressed in mol) (Ley et al. 2005). Litchfield (1993) suggested that the C:N:P ratio
in practice is 100:10:2. Oxygen is often added to contaminated sites to stimulate
aerobic degrading bacteria. In some cases, the degradation of specific organic
compounds in groundwater occurs under aerobic conditions. In such conditions,
dissolved oxygen will decrease, so the introduction of oxygen is required. The
literature contains reports showing that aerobic conditions are indicated by
dissolved oxygen concentrations exceeding 2 mg/L. In practice, on-site air sparging
of water can supply 8 mg/L dissolved oxygen, sparging with pure oxygen can
deliver 40 mg/L, while the application of hydrogen peroxide can provide more
than 100 mg/L oxygen. Therefore, while air sparging is the simplest and most
common oxygen delivery technique, the use of oxygen or hydrogen peroxide may
speed the bioremediation process and decrease the pumping required. However, in
some cases the increased cost and potential explosion hazard associated with a pure
oxygen supply may limit the applicability of direct oxygen use (NRC 1993).
Biodegradation of organic contaminants takes place under anaerobic conditions.
In such conditions, the availability of electron acceptors instead of oxygen should be
considered. Nitrate/nitrite, manganese, iron (III), and sulfate are electron acceptors
under anaerobic conditions.
In the case of coastal groundwater contaminated by landfill leachate–seawater
mixtures, sulfate is abundant. This suggests that the occurrence of organic
Table 5 Types of osmolytes

Group Types
Mono-di-oligo- Glucose, fructose, sucrose, raffinose and fructans
polysaccharides
Polyol (sugar alcohol) Sorbitol, manitol, glycerol,inositol and methylated inositol
Amino acid Methyl-proline,prolin betaine, ß-alanine betaine, choline
O-sulphate
Tertiary sulfonium Dimethylsulfoniopropionate (DMSP)
biodegradation should take place under sulfate-reduction conditions. A studied

reported by Mangimbulude et al. (2016) showed that high sulfate concentrations
were observed in landfill leachate and groundwater in comparison to other redox
elements. That study also showed high concentrations of H2S and Fe2+ in landfill
leachate and groundwater, indicating that sulfate-reduction and iron-reduction were
the dominant processes in the groundwater.
In the literature, for the biodegradation of contaminants in groundwater under
anaerobic conditions, organic substrates (such as molasses, lactate, butyrate, meth-
anol, ethanol, sodium benzoate) are often added as electron donor sources to enhance
biodegradation rates. In addition, whey, vegetable oils, and compost are also used as
organic substrates (EPA 2013).
Coastal groundwater contaminated by leachate–seawater mixtures at high organic
contaminant and high saline concentrations creates high osmotic conditions. In such
conditions, the addition of osmo-protective compounds (osmolytes) is important for
protecting microbes (Slama et al. 2015). Several osmolyte compounds have been
identified (Table 5) (Rhodes et al. 2002; Ashraf and Foolad 2007).
Factors to Consider
As noted earlier, the coastal groundwater status in some parts of low- and lower-
middle-income ASEAN countries is in a critical condition because it has been
contaminated. Cleaning up contaminated groundwater has become a mandatory
task of governments to be implemented by government self or by offering to
collaborated partners (practitioners or companies) but still under governments
supervision.
Bioremediation appears to be a feasible cleanup option. It involves relatively
low-cost, low-technology techniques that generally have high public acceptance and
can often be carried out on site. However, there are some challenges that should be
considered before applying bioremediation technology to coastal groundwater pol-
lution. According to Zurbrügg (2002), in many cities of Asia, deficiencies in the
provision of waste removal services are the result of inadequate financial resources,
an absence of management, and lacking technical skills of municipalities and
government authorities to deal with the rapid growth in the demand for services. The
Asia Development Bank Institute (1998) reported that the main challenges facing
local authorities in low-income Asian cities are as follows:
• Unplanned growth and increasing pressure to provide services

• Lack of adequate authority to address human, infrastructure, and resourcing
problems
• Bureaucratic confusion and delays due to a multitude of agencies (local, provin-
cial, and national levels) operating within the same municipal boundaries
• Lack of accountability
• Limited communications within the city administration and, more importantly,
between the city administration and the various stakeholders
• Political interference: elected representatives often do not confine themselves to
strategic planning, policymaking, and oversight of performance but instead
become involved in daily operations
• Lack of skills among municipal workforces; training is often reserved to senior
staff and seen as a reward for good work and as a chance to break away from daily
obligations
These challenges are important to know about and should be minimized to ensure
that the local authority’s (government’s) bioremediation strategic policy will con-
tinue to implemented.
Another factor is site characterization, as we know that site characterization is an
initial step toward making a plan for the application of bioremediation techniques. A
failure to take this step will affect subsequent planning. It should be noted that the
main factor in the characterization of groundwater sites in coastal areas is the
intrusion of saline seawater into groundwater due to tidal effects and the rise in
seawater levels. In such conditions adequate techniques involving the selection of
the appropriate microbes that are capable of degrading contaminants under high
osmotic conditions. Recently, haloarchaea and halobacteria species have been used
for the bioremediation of groundwater containing nitrogenous and aromatic hydro-
carbon compounds (Bonete et al. 2015).
Further research on anaerobic haloarchaea and halobacteria will be necessary in
order to find the appropriate microbes to use as biological agents in bioremediation
in coastal groundwater contexts. It is conceivable that, someday, organic contami-
nants in groundwater will be removed by means of biodegradation, but whether
saline groundwater can be remediated remains an open question. It seems that
intrinsic bioremediation technology (natural attenuation) is suitable for application
in the low-income ASEAN context because relative low-cost of operational and do
not requires many expert people, as far as operational system was established. Some
studies in the literature have reported on the attenuation of organic and inorganic
compounds separately. Thus, it is necessary to further study processes of natural
attenuation of organic and inorganic compounds in coastal groundwater contami-
nated by landfill leachate–seawater mixtures.
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Bacterial Cell-Mineral Interface, Its Impacts
on Biofilm Formation and Bioremediation 21
Hamid M. Pouran
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536
A Brief Description on the Minerals and Bacterial Cells Characterization Techniques . . . . . . . 539
XRD (X-Ray Diffraction) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 540
Infrared or IR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541
XPS (X-Ray Photoelectron Spectroscopy) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 542
AFM (Atomic Force Microscopy) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 543
Potentiometric Titration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 543
Effects of the Metal Oxides Surface Charge and Hydrophobicity on the Biofilm
Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 552
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 554
Abstract
This chapter aims to provide a better understanding of the bacterial cell attach-
ment and biofilm formation on the mineral surfaces, which would result in
improving our knowledge about: the interfacial forces governing the bacterial
cell attachment, predicting trends of the biofilm formation and consequently
biodegradation rates, and the contaminant’s fate in the diverse geological media
(Pouran HM. Studying molecular and nanoscale interactions at metal oxide
surfaces and their effects on bacterial adhesion, 2009).
In both aqueous and terrestrial environments, bacterial cells tend to be attached
to a surface and form biofilm. If they are associated to, e.g., a mineral surface,
bacterial cells would remain in a more stable microenvironment instead of being
removed by the water shear stress. Even the bacterial planktonic phase can be
considered as a mechanism for translocation from one surface to the other rather
H. M. Pouran (*)
Faculty of Science and Engineering, University of Wolverhampton, Wolverhampton, UK

https://doi.org/10.1007/978-3-319-73645-7_80
536 H. M. Pouran
than a prime lifestyle (Watnick and Kolter 2000; Young 2006). The biofilm
formation, which completely covers the surface, initially begins by the adhesion
of a small quantity of cells (Vadillo-rodri et al. 2006; Pouran et al. 2017).
Among the different indigenous microbial species in the contaminated envi-
ronments, some are capable of degrading pollutants and participating in the
environmental remediation process. The bioremediation process of the contami-
nated soils and waters is often considered a promising low risk management tool.
Even when the contamination poses an imminent threat and other approaches are
essential, bioremediation often is a viable secondary strategy for the site mainte-
nance (Haws et al. 2006; Pouran et al. 2017).
Natural environments are dynamic and complex systems; therefore, charac-
terization and identifying the underlying processes governing the contaminant’s
fate are not easy. Examples of the natural environments heterogeneity are the
diverse physicochemical properties of the soils and aquifers matrices (Stumm and
Morgan 1996). As the soils and sediments are the prime surfaces for the bacterial
cell attachment in most natural environments, elucidation of the surface proper-
ties of these constituents and their role in initiating cell adhesion and biofilm
formation are of the key importance in understanding the bioremediation process.
In fact, the cell-mineral interface reactions not only influence the biodegradation
process but many natural phenomena are affected by them.
Understanding role of physicochemical interactions at the bacterial cells and
minerals interface in the cell adhesion (as well as biofilm formation, develop-
ment, and behavior) is essential for planning effective bioremediation tech-
niques. It could potentially help us to predict the contaminants’ fate, and
trends of the biodegradation rates in different environments. Consequently, the
improved knowledge of the cell-mineral interface enable us to design and apply
more sophisticated bioremediation techniques as a viable approach towards
tackling the soil and water environmental pollution problems. Figure 1 schemat-
ically represents an aquifer and biofilm formation on some of the most abundant
minerals in the environment, iron and aluminum oxides. It also indicates some
the major effects of cell-mineral interface interactions on different environmental
processes (Stumm and Morgan 1996; Zachara and Fredrickson 2004; Cornell
and Schwertmann 2003).
Keywords
Bacterial cell-mineral interface · Biofilm · Bioremediation · Microenvironment ·
Planktonic phase
Introduction
Bioremediation can be described as a mechanism in which microorganisms degrade

pollutants in the environment. Such biodegradation can occur naturally or through
human managed processes, which aim to engineer bioremediation to enhance its
efficiency through different techniques, e.g., introducing new bacterial species to a
contaminated aquifer (Pouran et al. 2014; Fingerman and Nagabhushanam 2016).
21 Bacterial Cell-Mineral Interface, Its Impacts on Biofilm Formation. . . 537
Fig. 1 The schematic representation of biofilm formation in aquifers. In the aquatic environments
iron and aluminum oxides are of the most common minerals and often precipitate on the surface of
other minerals (e.g., quartz). A series of biogeochemical phenomena are influenced by the reaction
at cell-mineral interface as seen in this figure
The chapter presented here is based on the understanding that mineral surface
properties influence the cell attachment and biofilm formation (Pouran et al. 2014;
Bos et al. 1999). Among different minerals in the environment metal oxides are of
the most important ones and are vital to many environmental and industrial pro-
cesses. Geochemical reactions at the metal oxides surfaces play key roles in many
environmental processes, e.g., environmental remediation and aqueous geochemis-
try (Fotovat et al. 2008; Al-Abadleh and Grassian 2003). They are formed due to
weathering of the primary minerals, and recombination of the released cations and
anions lead to formation of the metal oxides, aluminum and iron oxides, which are
the most widespread minerals belonging to this group (Stumm and Morgan 1996;
Dixon and Weed 1992). These metal oxides have relatively high point of zero
charge (PZC), pH in which the surface charge is neutral, which make their surface
positively charged in pH range of most of the natural environments (Schwertmann
and Cornell 2008).
538 H. M. Pouran
Among all minerals and in particular the metal oxides, hematite, goethite, and
aluminum hydroxides are of the most common ones in soils and aquifers which often
appear in forms of coating on other mineral surfaces (e.g., quartz). In addition, they
have relatively high PZC. Considering the electrostatic interactions as an important
factor in initiating the cell adhesion (Bayoudh et al. 2006) and the electrostatic
attraction between positively charged metal oxide surfaces and negatively charged
bacterial cells, the above mentioned metal oxides are potentially good candidates to
study the cell-mineral interactions. Like metal oxides the bacterial cells also carry a
pH-dependent surface charge at the cell water interface. This surface charge stems
from the associated functional groups to the cell wall which their protonation/
deprotonation steps generate a pH-dependent surface charge (Pouran et al. 2017;
Claessens et al. 2006). However, the published research overwhelmingly suggests
that the bacterial cell surface has an overall negative charge in the pH range of the
natural environments (Pouran et al. 2014; Ojeda et al. 2008).
There are indications about the role of the surface hydrophobicity and charge of
both the cell surface and substrata in initiating cell adhesion; however, discrepancies
are found between the theoretical predictions and final steps of the cell attachment
(Pouran et al. 2014; Bayoudh et al. 2006). In principle hydrophobicity can be defined
as when the static water contact angle θ is >90 . A surface would be considered
hydrophilic when θ is <90 (Law 2014). Figure 2 shows a water drop contact angle
on hydrophobic polystyrene and hydrophilic hematite surfaces.
Cell attachment and the attached growth are influenced by the bacterial cell
growth microenvironment conditions. Carbon source is one of the variables that
affects the cell growth and biofilm formation. It can also to some extent influence the
cell surface properties, e.g., hydrophobicity as well as the cell wall macromolecules
Fig. 2 Water drop contact angle on hydrophobic polystyrene and hydrophilic hematite surfaces
and their physicochemical functions (Pouran et al. 2017; Geoghegan et al. 2008;
Andrews et al. 2009).
The aim of this chapter is to briefly talk about the cell-mineral interface forces
with focus on electrostatic and hydrophobic interactions. Other influential factors in
the microenvironment like the carbon source, though important, are not discussed
here. This chapter also briefly describes some of the most common techniques that
are used to characterize minerals, some of which could be used to analyze the
bacterial cells too.
A Brief Description on the Minerals and Bacterial Cells

Characterization Techniques
This section is a brief description on some of the important methods used to identify
and characterize minerals and analyze their surface properties. Some of them are also
used to determine physicochemical nature of the bacterial cell surface. These
methods include diffractometry, spectroscopy, microscopy, and potentiometric
titration.
Diffraction techniques involve interaction of radiation with the atoms of a solid.
X-ray diffraction, electron diffraction, and neutron diffraction belong to this group.
Among the diffractometery methods for mineral characterization X-ray diffraction
by far is the most widely used (Schwertmann and Cornell 2008).
Spectroscopy methods produce spectra when matter absorbs and emits electro-
magnetic radiation with specific energy (wavelength) (Dean et al. 2002). Infrared
(IR), ultraviolet-visible (UV-Vis), and X-ray photoelectron spectroscopy (XPS) are
of widely applied techniques in this group.
Infrared spectroscopy is an experimental tool for obtaining information about
chemical structure. Molecules can absorb infrared light of frequencies that match the
energy of changes in molecular vibrations. Infrared spectroscopy is therefore often
also called vibrational spectroscopy. This absorption of light can be very useful
because functional groups (such as O-H and C=O bonds) will often absorb infrared
light in a small range of frequencies regardless of other structural features. This is
one the standard techniques to characterize cell wall functional groups of the
bacterial cells (Pouran et al. 2013). UV-VIS spectroscopy uses light in the visible
and adjacent near ultra violet (UV) ranges, and its spectrum is a graph of light
absorbance versus the applied wavelengths. It is a routine technique for quantitative
measurements and is usually used for molecules and inorganic ions or complexes in
solutions. XPS method is used to determine chemical composition of material
surfaces. It uses the fixed energy source to excite electrons from the sample and
then measures their kinetic energy. Since their kinetic energy is dependent on their
binding energy different chemical species can be identified based on their distinct
binding energies (Pouran et al. 2014).
Optical microscopy, transmission electron microscopy (TEM), scanning electron
microscopy (SEM), scanning tunneling microscopy (STM), and atomic force
microscopy (AFM) constitute the major group of microscopy techniques for
540 H. M. Pouran
minerals and bacterial cells characterizations. Optical microscopes are the most
widely used type of microscopes and the important feature of them is that samples
can be easily analyzed in air or water.
TEM application for imaging enables us to obtain 2D images in magnification of
angstrom range; in this technique a beam of electron which is focused on a specimen
provides the enlarged image. For the TEM application the specimen must be very
thin and able to withstand the high vacuum present inside the instrument. There are
some disadvantages for this technique of which extensive sample preparation and
relatively small field of view are among them. The SEM technique is considered
almost as routine as optical examination with a light microscope. SEM is probably
the most universally useful technique available for the study of grain shapes and
physical characteristics of solid surface. It has a large depth of field and an enormous
magnification range, capable of image resolution from light microscope capabilities
down into the 10–20 angstrom range. SEM images have the 3D appearance which
makes them useful for evaluation of the surface structure of the sample. The STM
works by scanning an electrical probe over a surface to detect a weak electrical
current flowing between the tip and the surface. STM can be used to scan areas as
large as several thousands of square microns, and as small as several square
nanometers. The application of STM to study surfaces over this wide range of
magnification is well established. Atomic force microscopy (AFM) has the power
to visualize nanoscale surface phenomena in three dimensions, manipulate and
modify individual molecules, and measure such properties as adhesion, stiffness,
and friction as well as magnetic and electric fields. The use of chemically modified
tips extends the technique to include chemical imaging and measurement of specific
molecular interactions. Improved optical methods complement probe images and are
capable of imaging films a single molecule thick (Rosoff 2002).
Potentiometry and titration are some of the most import techniques in analytical
chemistry. The potentiometry involves measuring the electrical potential which is
related to component of interest. The measured potential may then be used to
determine the analytical quantity, generally the concentration of some component
of the analyte solution. Titrations are most commonly performed either to find out
how much analyte is present or to measure equilibrium constants of the analyte. The
necessary information for both purposes can be obtained by monitoring the pH of
solution as the titration is performed. Integration of these two techniques leads to
potentiometric titration which is measuring the potential of component of interest as
a function of added reagent volume. In minerals and bacterial cells characterizations
potentiometric titration is performed to determine mineral or the strain surface
charge in aqueous medium.
XRD (X-Ray Diffraction)
X-ray region encompasses both “hard” X-rays (wavelengths down to 10 nm) and
less penetrating “soft” X-rays (wavelengths up to 10 nm) with optical frequencies
lying between 3 1019 and 3 1016 Hz and the capacity to produce ionization by
electron detachment. The photon energies in this region are often reported in electron
volts (eV), and run from around 105 eV down to 100 eV (1 eV = 1.602 1019 J).
X-ray crystallography is a fundamental and one of the most useful techniques for
exploring the nature of synthetic and natural matters. X-ray diffractometry (XRD) is
used to determine the phase content in many minerals and materials. Since the
discovery of Bragg-type X-ray diffraction (Eq. 1) from periodic crystal lattices, the
technique has proven an essential tool for the identification of crystalline com-
pounds. Such routine applications have developed during the first half of the
twentieth century into standard analysis procedures, and during the last decades
they became so widely utilized that data are now available for most known inorganic
compounds and minerals.
nλ ¼ 2d Sin θ (1)
Equation 1. Bragg’s law for the X-ray diffraction patterns. In this equation, n is an
integer, λ is the wavelength of X rays, d is the spacing between the planes in the
atomic lattice, and θ is the angle between the incident ray and scattering planes.
The analysis of the atomic structure of crystals by diffraction is one of the more
developed applications in the whole field of diffraction. Although often used as a
simple, rapid technique for molecular structure determination, the full analysis of
the crystal structure by X-ray diffraction indeed represents a powerful tool for the
detailed interpretation of the relationship between the long-range atomic arrange-
ment and the physicochemical properties in any solid-state material. In general
terms, it is used in a wide range of disciplines as an adjunct to chemical analysis in
the identification of the constituents of crystalline phases (Lindon et al. 2000;
Wang 2000). Examples of XRD advantages are: relatively easy sample preparation,
rapid measurements, analysis of mixed phases, and availability of large database
for diffraction patterns of diverse materials. In addition, this technique potentially
can help us to determine particle’s dimensions for crystalline materials. On the
other side, need for well-ordered crystals and sufficient materials are of its
disadvantages.
Infrared or IR Spectroscopy
Infrared (IR) spectroscopy has been for decades a frequently used method to
investigate the structure, bonding, and chemical properties of minerals and bacterial
strains (Pouran et al. 2013, 2017; Madejova 2003). This method is related to the
energy changes involved in the stretching and bending of covalent bonds in mole-
cules. A covalent bond between two atoms can be modeled as a spring connecting
two masses. The frequency of the spring vibration is calculated by Hook’s law
(Eq. 2).
rffiffiffi
1 κ
υ¼ (2)
2π μ
542 H. M. Pouran
Equation 2. Hook’s law equation relates the frequency of vibration (ν) to the
strength of the spring.
In this equation ν is the frequency of vibration, к is the force constant (the strength
of spring), and μ is related to the masses on the end of spring which is defined as the
reduced mass (Eq. 3).
μ ¼ ððm1 m2 Þ
ðm1 þ m2 ÞÞ (3)
Equation 3. This equation is related to the masses on the end of the spring (m1 and
m2) and used to calculate the reduced mass μ for the Hook’s equation.
According to Hook’s equation when the bond between two atoms changes from
single to a double and then a triple bond, the vibration of bond increases respectively
(spring gets stronger). As the masses of the atoms on the bond increases the
frequency of vibration decreases. The entire infrared region includes wavelengths
range from 700 nanometers to 1 millimeter. The value of IR spectroscopy is greatly
enhanced by Fourier transformation. It is a reliable method for observing the entire
spectrum at once and referred to as Fourier transform spectroscopy or FTIR. Fourier
analysis is a procedure in which a curve is decomposed into a sum of sine and cosine
terms, called a Fourier series. To analyze a curve which spans over the interval x1
and x2, the following equations can be used.
X
1
y¼ ½an sin ðnωxÞ þ bn cos ðnωxÞ (4)
n¼0
Equation 4. In this equation y is Fourier series, ω is phase amplitude, and a and

b are Fourier coefficients.
2π
ω¼ (5)
x2 x1
Equation 5. Calculation of phase amplitude between two points x1 and x2 over the
x axis.
Some of the advantages of using FTIR are: requirement to minimal sample prep-
aration prior to spectral measurements, rapid scanning speed, and enhanced sensitivity
(Lindon et al. 2000; Dean et al. 2002). There are also some limitations about using
FTIR, for instance in experiments, which may take a long time, any changes in infrared
absorbing gas concentrations (e.g., carbon dioxide) in the ambient environment may
influence the results. It does require collecting blank and in ATR-FTIR, sample must be
in contact with ATR crystal, which may damage the sample’s surface.
XPS (X-Ray Photoelectron Spectroscopy)
X-ray photoelectron spectroscopy is a standard, widely used and sensitive technique

to analyze atomic compositions of the solid material’s surface (first few atomic
layers). This approach can help us to identify the elements at the surface and quantify
them (except hydrogen and helium). It relies on measuring the kinetic energy of
emitted electrons from the sample’s surface by using an energy sensitive detector.
Atoms at the surface are excited with X-ray and if the radiation is strong enough they
can escape from the material. In XPS analysis irradiation causes a core electron to be
ejected. Each element core electrons have specific binding energies which are
characteristic of that element. In this respect, given the irradiation beam energy is
known, measuring kinetic energy of the excited electrons help us to analyze atoms
present at the material’s surface. This information reveals both elemental and
chemical bonding information of a sample surface. The ability to analyse a broad
range of materials’ surfaces e.g. polymers and metals, including quantitative
analysis and determining the samples chemical states are some of XPS technique
advantages. High sensitivity to external contamination on the sample (sample
handling, e.g., finger print), relatively small analytical area, and analysis depth in
addition to operation costs are some of XPS analysis limitations.
AFM (Atomic Force Microscopy)
AFM consists of a small lever of submillimeter dimensions. At the end of this

cantilever is a sharp tip used to probe the interactions with a given sample. The
lever on which the tip is mounted will change its position, its apparent frequency, and
stiffness according to the interaction with the surface. These changes can be sensi-
tively measured by detecting either the static or dynamic motion of the lever with the
sub angstrom sensitivity. This is usually done by optical beam deflection. With this
system, light from a laser diode or light-emitting diode is reflected from the back of
the cantilever onto a four-segment photodiode. As the cantilever bends, the reflected
beam moves across the photodiode, thus altering the relative voltages from each
segment. It is then possible to analyze this to give normal and torsional motion of the
cantilever (Rosoff 2002). Because of its high sensitivity AFM has become one of the
foremost tools for imaging, measuring, and manipulating matter at the nanoscale. It
has made it possible to evaluate molecular and surface interactions in liquid as a
function of the surface separation. AFM has revolutionized the surface and interface
sciences by allowing direct measurement of the surface and intermolecular forces
with near molecular scale resolution (Vakarelski and Higashitani 2006). With respect
to imaging rapid sample preparation, ability to perform analysis in different envi-
ronments (e.g., aqueous and air), providing a true 3D image of the sample, and
availability of a range of specifically designed probes for different purposes are some
of atomic force microscopy advantages. On the other hand, limited scanning area
(specially compared to Scanning Electron Microscopy) and presence of the image
artifacts due to incorrect choice of the tip are main AFM disadvantages.
Potentiometric Titration
The metal oxide minerals and bacterial cells both have pH-dependent surface charge.
The pH at which the absolute value of surface charge becomes equal to zero is
544 H. M. Pouran
defined as point of zero charge (PZC) (Stumm and Morgan 1996). In pH of PZC
(pHpzc) equal adsorption of potential determining cations and anions at the surface
occurs. In aqueous medium H+ and OH are the potential determining ions, and the
created surface charge on the metal oxides is the result of protonation and
deprotonation of surface hydroxyl groups. While in the bacterial cell walls a range
of functional groups exit, for example, carboxyl, hydroxyl, and amines. One of the
prime techniques that can measure PZC is potentiometric titration.
The surface charge causes the development of a potential, which extends from the
surface to the bulk solution where it takes zero value. It can be extended from several
angstroms to several nanometers (Bourikas et al. 2006). It is assumed that the surface
potential follows the Nernst equation and for any colloidal particle is given by
equation 6 (Klabunde 2001).

Ψ0 ¼ 0:059 pH pH pzc (6)
Equation 6. This equation shows calculation of surface potential for any colloidal
particle.
In electrochemistry Nernst equation defines the equilibrium potential of an
electrode (Eq. 7).
E ¼ E0 þ RT=nFlogefHg (7)
Equation 7. The Nernst equation is used to calculate electrode potential.

In the above equation E0 is called standard electrode potential, R is the gas
constant, T the absolute temperature (K), F the faraday constant, n = 1 in the case
of glass electrode, and {H+} shows hydrogen ion activity. Under high ionic medium
conditions (ionic medium scale) the activity coefficient is assumed to be unity
(Stumm and Morgan 1996). If we convert the natural logarithm in Eq. 7 to base
10 logarithm and insert T = 298.15 K (25.00 C), we can obtain the modified Nernst
equation (Eq. 8).
E ¼ E0 þ slog10½H (8)
Equation 8. Modified Nernst equation can be used to determine glass electrode

potential.
In the modified Nernst equation, E is the glass electrode potential, E0 is the
standard electrode potential, and S is the slope which should be close to the ideal
value of 59.1 in 25 C (Stumm and Morgan 1996; Gans and O’Sullivan 2000). To
calculate PZC the aqueous suspensions of minerals or bacterial cells (should be in
freeze dried form) are titrated against strong acid and base. Changes in solution pH
are recorded versus the added volume of acid or base. The titration data are
interpreted based on proton adsorption to the mineral mass during titration. To
perform potentiometric titration, acid and base are required to get prepared in
advance. Other essential steps for titration are preparing electrolyte and pH electrode
calibration. Figure 3 schematically shows the interface between a metal oxide,
Bacterium cell surface
Hydrophilic surface group (e.g. hydroxyl)
Hydrophobic surface groups (e.g. some of proteins)
+ Ψ
Surface potential (mV)

Fe3+
+ + + + + + + + + +
+ + + + + + + + + +
+ +
Fe3+ Fe3+ Fe3+ Fe3+ Fe3+ Fe3+
Distance (nm)
Fe3+ Fe3+
Hematite-water interface in pH below point of zero charge
Fig. 3 Schematic representation of the hematite and bacterial cell interface with respect to the
surface charge and hydrophobicity. The hematite surface charge (mv = millivolt) exponentially
decays by increasing the distance from the mineral surface (nm = nanometer). As seen the metal
oxide has a hydrophilic surface and the bacterial cell has both hydrophobic and hydrophilic moieties
hematite in this case, and a bacterial cell. As seen the hematite surface is hydrophilic
while the bacterial cell wall has both hydrophilic and hydrophobic components
(because of the cell wall, macromolecules could be either hydrophilic or
hydrophobic).
Effects of the Metal Oxides Surface Charge and Hydrophobicity

on the Biofilm Formation
In this part, results of some of the recent studies that have evaluated biofilm
formation of genetically diverse hydrocarbon-degrading bacteria on iron and alu-
minum oxides are reported. These studies are important as they have been
performed on the mineral surfaces, which have been prepared in a compatible
method to naturally occurring deposition of the metal oxide colloidal particles. As
mentioned before iron and aluminum oxides, especially hematite, goethite, and
aluminum hydroxide, are ubiquitous and of the most abundant minerals. They often
appear in form of naturally occurring colloidal particles deposited on other mineral
surfaces for example quartz (Stumm and Morgan 1996; Schwertmann and Cornell
2008). In aquifers quartz surfaces coated with fine yellowish goethite or reddish
hematite spots are abundant. Studies of biofilm formation on the mineral surfaces
546 H. M. Pouran
are not new, but they have been performed on precisely engineered surfaces, for
example, using techniques like chemical vapor deposition that allows deposition of
a thin layer of certain metal oxide on a base layer. The mineral surfaces affect
adhesion of single planktonic bacterial cells, which upon attachment can form
extensive biofilms. It is well established that the extent of biofilm formation is
correlated with the biodegradation process, which is a cost-effective method to
clean up contaminate aquifers.
Iron and aluminum oxides have pH-dependent surface charge. Their point of zero
charge (PZC) is about or above pH of most of the natural environments. On the other
hand, bacterial strains in most cases have relatively low point of zero charge, often
around 4.5. Theoretically strong electrostatic interactions between positively
charged metal oxides and negatively charged bacterial cells are expected in the
natural environments. Nevertheless, there are other complexities that may hinder
this electrostatic attraction, namely the aqueous medium ionic strength. Ionic
strength (IS) is a measure of the total ion concentrations in a solution and reflects
the strength of the electric field. To calculate the ionic strength the ions with more
charge are counted more because of their stronger electrostatic influence. As seen in
Eq. 9, ionic strength considers square of the ions charges.
1
I¼ ΣCi z2i (9)
2
Equation 9. Calculating the ionic strength in a solution based on the ions
concentrations and charges. In this equation, I = ionic strength, Ci = concentration
of ith ion, and Zi = charge of the ith ion.
Figure 4 schematically shows charge distribution around a single bacterial cell
(in its planktonic form). As seen in this figure Zeta potential (ζ) is the electrical
potential difference at the shear plane that is the interface between the bulk aqueous
medium and static fluid layer attached to a bacterial cell (Martinez et al. 2008).
As depicted in Fig. 4 surface charge of a charged particle, in this case a bacterial
cell, is not homogenous and what we consider as positive or negative surface charge
is the overall charge of the surface. Immediately after the bacterial cell (charged
particle) surface there is a layer called Stern, which refers to the adsorbed ions on the
surface. After the shear plane that indicates the zeta potential, we have diffuse double
layer, which decays with the increasing the distance from the surface. The length of
diffuse double layer (DDL) is inversely proportion to the solution ionic strength. In
other words, the higher ionic strength leads to the lower length of diffuse double
layer from the charged particle surface. As schematically depicted for the cell and
mineral surfaces in Fig. 5, increasing the ionic strength decreases the diffuse double
layer length and the impact of surface potential over a known distance (regardless of
the nature of the surface charge). Consequently, for the higher IS values not only zeta
potential is reduced but the effective distance from the surface over which electro-
static interactions can operate is shortened. As figure 5 shows changes in the metal
oxide surface potential by increasing ionic strength are compatible with the impacts
that we see for the cell surface potentials. Regardless of this similarity in trend, the
Fig. 4 Schematic
representation of distribution
of electric charges and
position of zeta potential
around a negatively charged
planktonic bacterial cell
metal oxides and bacterial cells have opposite surface charges in the pH range of
most of the natural environments.
One of the methods that have applications in studying bacterial cells adhesions is
a theory called DLVO. This colloidal stability theory was developed by four
scientists, Derjaguin, Landau, Vervey, and Overbeek (DLVO), and aims to explain
the interactions between colloidal particles and their aggregation behavior. This
approach can be used to study adhesion of colloidal biological microorganism
onto different surfaces as a qualitative or quantitative model (Hermansson 1999).
The classical DLVO theory has also been modified to be more inclusive in calculat-
ing the adhesion energy. This modified DLVO method is known as extended-DLVO.
In principal in the biofilm formation research the classical DLVO theory attempts to
explain the interaction between a flat surface and a cell, as a balance between two
additive factors: van der Waals (vdW) interactions and attractive or repulsive
interactions from the overlap of the electrical double layers of the cell and surface
(Hermansson 1999). Van der Waals (vdW) forces refer to the distance-dependent
intermolecular forces (it also may happen between atoms). This general term is used
for relatively weak attraction forces between molecules. The extended DLVO
method in addition to the forces included in the classical DLVO considers hydro-
phobic interactions between the two surfaces as well as electron-donating accepting
nature of the materials.
The electrostatic behavior of the bacterial surfaces is considerably more complex
than minerals. Presence of different types of biopolymers at the cell surface, which
can undergo conformational changes, directly influences bacterial cell surface elec-
trostatic profile (Hong and Brown 2008). Bacterial polyelectrolytic polymeric layers
that extend out of the cell wall can function like anchors and aid the adhesion when
548 H. M. Pouran
Fig. 5 Schematic
representations of changes in
the surface potentials by
altering the ionic strength. In
these illustrations, the
bacterial cell and the mineral
surfaces are assumed to
respectively have negative
and positive charges. Also,
variations of the diffuse
double layer (DDL) of a
charged particle because of
the solution ionic strength are
shown
the cell approaches a surface (Hong and Brown 2008; Bergstrom et al. 2006). These
surface polyelectrolytes can experience conformational changes due to changing
solution chemistry, specifically ionic strength and pH (Redman et al. 2004). The
presence of protons (low pH values) and/or high ionic strengths can change cell
surface polymers from stretched to coiled forms as well as altering the rigidity of
these macromolecules. In an opposite way, increasing pH and decreasing ionic
strength leads to increasing ionization of the biopolymers and electrostatic interac-
tion (repulsion) between the side chains. These nonscreened electrostatic interac-
tions cause lack of conformational stability of the surface polymers and random
shape polymer structures (Fedorov et al. 2009).
As described above, the electrostatic and hydrophobic interactions between the
cell and mineral surfaces play key roles in the cell adhesion and biofilm formation.
Moreover, the expected electrostatic attraction between positively charged metal
oxide surfaces and negatively charged bacterial cells make the before-mentioned
metal oxides, hematite, goethite, and aluminum hydroxide, potentially good candi-
dates for studying the cell-mineral interactions. Here the results of a series of
experiments that have studied the role of surface charge and hydrophobicity of the
mineral surfaces on the cell adhesions are reported. In these researches the minerals
are iron and aluminum oxides, and the cells are six genetically diverse hydrocarbon-
degrading bacterial strains isolated from contaminated environments (Pouran et al.
2009, 2014, 2017).
For these studies, hematite was synthesized by heating an acidic solution of
FeCl3, goethite was prepared by heating an alkaline solution of Fe(NO3)3, and to
prepare Al(OH)3, aluminum nitrate was added to an alkaline solution. The synthe-
sized minerals were analyzed by an X-ray powder diffractometer and FTIR imaging
system. To determine the point of zero charge (PZC) of the synthetic metal oxides,
potentiometric titration was performed using an automated potentiometric titrator. To
obtain the surface hydrophobicity of the synthetic minerals, the water-drop contact
angles in the air were measured based on the sessile drop method, which is
measuring the contact angle between the surface and a tangent drawn on the drop
surface, passing through the triple point of atmosphere–liquid–solid. The cells
surface hydrophobicity was obtained by using MATH (Microbial Adhesion To
Hydrocarbon). In this test, bacterial cell attachment to hydrocarbon droplets deter-
mines the hydrophobicity of the sample.
To prepare mineral surfaces in a compatible way to naturally occurring process of
deposition of metal oxide colloidal particles on the available surfaces in aquifers, a
reference (base) material (polystyrene) was coated by direct deposition of the
synthesized hematite, goethite, and aluminum hydroxide particles from aqueous
suspensions by evaporations, and the details of this coating method can be found
in previous publications (Pouran et al. 2009, 2014). Properties of the coated surfaces
were analyzed by using optical microscopy, water drop contact angle measurements,
ATR-FTIR, and XPS and proved that these prepared surfaces have similar physico-
chemical properties to the initially synthesized reference minerals.
The bacterial strains in these studies were isolated from contaminated soils and
aquifers. These genetically diverse cells belonged to Rhodococcus spp. (RC92 and
550 H. M. Pouran
RC291), Pseudomonas spp. (Pse1 and Pse2), and Sphingomonas spp. (Sph1 and
Sph2) groups. These cells were grown in a defined medium, known as AB10
(IS 200 mM) (Pouran et al. 2014, 2017). These strains were added to the reference
surfaces (12 well-plates), which were completely coated with the synthesized min-
erals. After 96 hours incubation at 25 C in AB10 medium (pH 6.5), each well was
gently washed with ultra-high quality water (UHQ). The wells were imaged using a
noninvasive in situ method. The attached cells were stained by a green fluorescent
nucleic acid stain and imaged using a water-dipping microscope objective. In
addition to imaging the attached growth, the planktonic phase of each of the bacterial
strains was evaluated after the incubation time.
The results suggest that reference surfaces studied in this research, polystyrene
(hydrophobic, no surface charge), hematite (hydrophilic, positive surface charge),
goethite (hydrophilic, positive surface charge), and aluminum hydroxide (hydro-
philic, positive surface charge), do not notably change the planktonic phase growth
of the cells. In other words, the level of cell growth in the planktonic phase seems to
be independent from the surface charge and hydrophobicity of the growing envi-
ronment’s surface. With respect to hydrophobic interactions, RC92 showed dis-
persed chain-shape biofilm on the hydrophobic polystyrene, while the other
hydrophobic strains, RC291 and Sph1, displayed considerable cell attachments.
Surprisingly Sph2 (hydrophilic) also showed extensive cell attachment on the
hydrophobic polystyrene surface. The same happened for the expected electrostatic
interactions; hydrophobic RC92, RC291, and Sph1 had negligible and poor attach-
ments on the positively charged hematite, goethite, and aluminum hydroxide sur-
faces (in the pH of the experiment 6.5). Hydrophilic Pse1 and Pse2 attachment
patterns were extensive as expected (because of electrostatic attractions between the
negatively charged bacterial cells and positively charged mineral surfaces). How-
ever, hydrophilic Sph2 showed an unexpected attachment behavior, good attachment
on neutral hydrophobic polystyrene and poor adhesion on the hydrophilic positively
charged metal oxides. The attachment behaviors of the studied strains and surfaces
are summarized in Table 1. The details of these studies as well as related images
depicting morphology of the biofilm formations have been provided in the previous
publications (Pouran et al. 2009, 2014, 2017).
The negligible attachments of hydrophobic RC92 and RC291 strains to the
hydrophilic minerals is not surprising; however, the differences in the adhesion
behavior of these two strains on the hydrophobic polystyrene suggest that other
factors affect this behavior. Such differences in the attachment patterns of these
strains are rooted in their surface macromolecules. Both cells have lipophilic mac-
romolecules at their borders with the ambient environments; however, the associa-
tion of these moieties with the cell wall is different. For RC92, though extracellular
lipophilic molecules exist at the cell wall, they can be easily detached from the cell,
and cannot function as strong anchors that keep the strain on the surface, while for
RC291 these macromolecules are closely associated with the cell surface (Pouran
et al. 2017).
For Pse1 and Pse2 similarities in their attachment patterns on the polystyrene
were observed, nevertheless, the number of Pse1 cells attached to the hydrophobic
Table 1 Adhesion morphologies of RC92, RC291, Pse1, Pse2, Sph1, and Sph2 to polystyrene and
mineral surfaces
Aluminum
Attachment Hematite Goethite hydroxide Polystyrene
Surface Hydrophilic Hydrophilic Hydrophilic Hydrophilic
Bacterial strain PZC = 7.5 PZC = 8.5 PZC = 8.9 Neutral
RC92 Negligible cell Negligible cell Negligible cell Dispersed
Hydrophobic, attachment attachment attachment chain-shape
PZC < 6.5 biofilm
RC291 Negligible cell Negligible cell Negligible cell Highly
Hydrophobic, attachment attachment attachment structured
PZC < 6.5 biofilm
Pse1 Extensive cell Extensive cell Extensive cell Sparse
Hydrophilic, clusters clusters clusters Micro-
PZC < 6.5 colonies
Pse2 Extensive cell Extensive cell Extensive cell Sparse
Hydrophilic, clusters clusters clusters Micro-
PZC < 6.5 colonies
Sph1 Poor, dispersed Poor, dispersed Poor, dispersed Extensive cell
Hydrophobic, single-cell single-cell single-cell attachment
PZC < 6.5 attachment attachment attachment
Sph2 Poor, dispersed Poor, dispersed Poor, dispersed Extensive cell
Hydrophilic, single-cell single-cell single-cell attachment
PZC < 6.5 attachment attachment attachment
polystyrene was notably higher than Pse2. Other studies suggest (Pouran et al. 2017;
Huang et al. 2008; Andrews et al. 2010) that for the Pseudomonas species the
extracellular DNA (eDNA) causes the difference in Pse1 and Pse2 attachment
patterns. The presence of eDNA enhances Pse1 adhesion to a hydrophobic surface.
The Sphingomonas strains, Sph1 (hydrophobic) and Sph2 (hydrophilic) biofilm
formations on the minerals and polystyrene surfaces are compatible. These strains
have glycosphingolipids (GSL) instead of lipopolysaccharide (LPS), which has an
amphiphilic nature and consists of both hydrophobic and hydrophilic parts. Presence
of glycosphingolipids is very likely the reason for their adhesion to both hydropho-
bic and hydrophilic surfaces. Nevertheless, Sph2 dispersed single-cell attachment
patterns on the minerals are in contrary with the expected electrostatic attraction
between these two hydrophilic entities in the pH of the experiment (6.5).
To study anomalies of Sph2 adhesion to the metal oxides, its zeta potential was
measured using a zeta potential analyzer (Sph2 strain suspended in 1 mM of KCl). The
results showed that this strain has a negative surface potential at circa neutral pH values.
This agrees with other research indicating that bacterial cells often have a relatively low
PZC and carry a negative surface charge in natural media; however, it does not explain
poor attachment of this strain on positively charged metal-oxide surfaces (Pouran et al.
2014; Claessens et al. 2006; Ojeda et al. 2008, b; Leone et al. 2007). As mentioned
earlier these studies were performed in AB10, which is a defined medium with ionic
strength (IS) of approximately 200 mM and as we know the high ionic strength
552 H. M. Pouran
Fig. 6 Biofilm formation of Sph2 on hematite surface under different ionic strengths (a; IS
200 mM, b; IS 100 mM, c; IS 20 mM)
hampers diffuse double layer surrounding the colloidal particles. To further investigate
role of ionic strength on Sph2 adhesion to the metal oxides, this medium IS was altered
by reducing its NaCl content, which has the highest concentration in AB10, to
approximately 100 and 10 mM. Measuring zeta potential of Sph2 in the original and
altered AB10 media indicated that surface potential of Sph2 in IS of 200 mM is close to
zero, for IS of 100 mM is approximately 5 mV and for IS of 20 mM is almost
20 mV. Such difference in the surface potential of Sph2 in AB10 medium with low
ionic strength should manifest itself in the adhesion behavior of this strain.
To further investigate Sph2 attached growth on the metal oxide in low IS, its
adhesion to hematite was evaluated under AB10 medium with approximately
200 mM (original AB ionic strength), 100 mM, and 20 mM, respectively. Interest-
ingly reducing the solution ionic strength to 20 mM led to 10 times increase in the
number of Sph2 attached cells. Figure 6 clearly shows changes in the Sph2 biofilm
formation pattern under different ionic strength conditions. It is worth mentioning
that changes in the solution IS also affects conformational changes of the cell wall
macromolecules; in lower IS these cell wall moieties can have random extended
shapes, act as anchors, and facilitate attachment, opposite to higher ionic strengths
when these macromolecules form coil-shaped appendages attached to the surface.
Summary
The cell-mineral interface plays a key role in initiating bacterial cell adhesion on
minerals. The attached growth of bacterial cells and biofilms formation on the
available surfaces in the environment starts with adhesion of single cells, which
find the attached form more favorable than planktonic style for interacting with their
ambient environment (O’Tool and Wong 2016). The bioremediation process, clean-
up of pollutants in the environment using microorganisms, is directly correlated to
the extent of biofilm formation. In other words, the more attached cells (biofilm
formed on the minerals) the higher rate of pollutants biodegradation is expected.
The bacterial strains and mineral surfaces each have their own unique physico-
chemical properties especially surface charge and hydrophobicity. For the bacterial
cells these characteristics are more complex due to the nature of these strains as
living microorganisms. Conformational changes in the cell wall macromolecules is
one of these examples. The mineral surfaces in the environment are also not pristine.
They are often covered (coated) by a range of fine particles that may have inorganic
or organic nature (or a combination of both).
The first step towards understanding the cell-mineral interface is to have proper
information about each of these components. In this chapter, many of the techniques
that can be used to characterize surface properties of the cells and minerals have been
briefly discussed.
Metal oxides especially iron and aluminum oxides are some of the most abundant
minerals in the environment. In soils and aquifers, they also appear in form of fine
particles deposited on different surfaces, quartz surfaces with hematite and goethite
coatings on them is a typical example. These minerals due to their ubiquitous
presence and relatively high pH-dependent surface charge are good candidates for
studying cell-mineral interactions under controlled environments.
Here also the results of a series of studies that had aimed at exploring the role of
electrostatic and hydrophobic interactions between the cell and minerals in biofilm
formation have been reported. Such information would be helpful for designing
better bioremediation processes, and predicting attenuation of the contaminants in
the affected sites. Studying biofilm formation of genetically diverse bacterial cells
isolated from contaminated environments on the iron and aluminum oxides indicated
that cell-adhesion predictions based on the effects of electrostatic and hydrophobic
interactions are likely to show discrepancies when compared to real attachment
behavior. The key role of the solution ionic composition and strength (IS) was also
discussed as one of the studied strains showed dramatically more attached cells on
hematite when the solution ionic strength was decreased.
For planning effective engineered bioremediation it is important to consider that
the presence of a high number of bacterial cells in the planktonic phase is not
necessarily a sign of extensive cell attachment and biofilm formation. In other
words, a realistic prediction of bioremediation is feasible if the physicochemical
properties of bacterial cells and mineral surfaces as well as the solution chemistry
and ionic strength of aquifer media are thoroughly characterized.
Cross-References
▶ Application of Novel Microbial Consortia for Environmental Site Remediation

and Hazardous Waste Management Toward Low- and High-Density Polyethylene
and Prioritizing the Cost-Effective, Eco-friendly, and Sustainable Biotechno-
logical Intervention
▶ Bioremediation of Hormones from Waste Water
▶ Bioremediation of Mined Waste Land
▶ Biostimulation and Bioaugmentation: An Alternative Strategy for Bioremediation
of Ground Water Contaminated Mixed Landfill Leachate and Sea Water in Low
554 H. M. Pouran
▶ Characterizing the Cell Surface Properties of Hydrocarbon-Degrading Bacterial

Strains, a Case Study
▶ Development of an Environmentally Sustainable Approach for Safe Disposal of
Arsenic-Rich Sludge
▶ Management of Radioactive Wastes
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Bioremediation of Mined Waste Land
22
Nisha Rani, Hardeep Rai Sharma, Anubha Kaushik, and
Anand Sagar
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 558
Environmental Impacts of Mining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 560
Strategies of Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
Physical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
Chemical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
Biological . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
Bioremediation: An Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
Principle of Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
Factors Affecting Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
Techniques in Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 565
In Situ Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 565
Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 566
Case Study: Kashlog Mining Area, Darlaghat, Solan, Himachal Pradesh, India . . . . . . . . . . . . . . 571
Soil Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
Isolation of VAM and Cyanobacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
Abstract
The economic development and ever growing industrialization has improved the
GDP and hence standard of living in the entire countries of the world. But all
these are accompanied with environmental degradation as a price of
N. Rani (*) · A. Sagar

Department of BioSciences, Himachal Pradesh University, Shimla, India
H. R. Sharma
Institute of Environmental Studies, Kurukshetra University, Kurukshetra, Haryana, India
A. Kaushik
University School of Environment Management, Guru Gobind Singh Indraprastha University,
Dwarika, New Delhi, India

https://doi.org/10.1007/978-3-319-73645-7_79
558 N. Rani et al.
development. Mining is very important next only to agriculture and also critical to
the development of a nation. So far, most mining activities have been unscientific
with scant respect for environmental protection. It effects the environment by way
of soil erosion (water and wind), soil salinization/alkalization/acidification, water
logging, etc. The damages to land go on increasing with accelerated rates and land
is degraded with their cumulative effects.
Land is most important basic natural resource and influences every sphere of
human activity. Soil sustains all life forms on the planet. Healthy soil is indeed
alive and is a complex and dynamic combination of geology, topography, hydrol-
ogy, soil, and flora and fauna, that is, minerals, bacteria, fungi, algae, protozoa,
worms, insects, etc. Land sources are limited and population size is increasing
day by day. To fulfill the requirements of ever increasing population, the pressure
is exerted on agriculture to supply future food and fiber needs. The agriculture
community is facing a great challenge to enhance the production. India occupies
2.4% of the global geographical area and shares 16% of human population and
15% of livestock population. This scenario has necessitated proper demarcation
of productive and nonproductive lands, particularly the wastelands that could be
treated and reclaimed for productive use. To meet the challenge, the focus is on
the restoration of degraded land and understands the complexities and interac-
tions of soil biological system and agro-ecosystem as a whole. Soil microorgan-
isms play an important role in reclamation of such degraded lands and have
important influence on soil fertility and plant health.
Keywords
Industrialization · Degradation · Salinization · Alkalization · Acidification
Introduction
Wastelands are synonymous with drastically disturb lands where the native vegeta-
tion and animal communities have been removed and the top soil has been lost,
altered, or buried. Such lands will not become naturally rehabilitated within the life
time of man through normal succession process. In India 14.91% of total geographic
area are wastelands under different categories. About 40.36% of total geographic
area in Himachal Pradesh falls under wasteland, out of which 7.46% is mining
wasteland (Sagar et al. 2015). Examples of wastelands are surface mined lands for
minerals (coal, kaoline, phosphate, bauxite, gravel, sand, etc.), mining wastes, top
soil removed for use elsewhere creating “borrow pits,” saline soils, wind and water
eroded site, snow covered and glacial area, and degraded forests (Chandra 1992).
Land is complex and dynamic combination of geology, topography, hydrology,
soil, and flora and fauna. It is a finite, nonreproducible consumption resource held as
a source of livelihood and a financial security transferred as wealth across genera-
tions. Mining sector is an important segment of the Indian economy and country is
endowed with huge resources of many metallic and nonmetallic minerals. Since
22 Bioremediation of Mined Waste Land 559
independence, there has been a pronounced growth in the mineral production both in
terms of quantity and value. India produces as many as 87 minerals, which includes
fuels, 10 metallic, 47 nonmetallic, 3 atomic, and 23 minor minerals (including
building and other materials).
The distribution of minerals in the country is uneven and mineral density varies
from region to region. Khullar (2006) identifies five mineral “belts” in the country:
The North Eastern Peninsular Belt, Central Belt, Southern Belt, South Western Belt,
and the North Western Belt. India is self-sufficient in minerals which constitute
primary mineral raw materials to industries, such as thermal power generation, iron
and steel, ferro-alloys, aluminum, cement, various types of refractory, china clay-
based ceramics, glass, chemicals like caustic soda, soda ash, calcium carbide,
titanium white pigment. India is, by and large, self-sufficient in coal (with the
exception of very low ash coking coal required by the steel plants) and almost all
the industrial minerals; lignite among mineral fuels; bauxite, chromite, manganese,
and iron ores; and ilmenite and rutile among metallic minerals.
Mining is very important next only to agriculture and also critical to the devel-
opment of a nation. So far most mining activities have been unscientific with scant
respect of environmental protection. Once the top soil and subsoil are lost, land
reclamation of open cast mines becomes difficult (Chandra 1992). In mining areas,
the soils are affected by various mining operations, that is, blasting, drilling, and
storage of overburden dump materials, clearing of land, construction of ancillary
facilities, and movement of vehicles (Sharma et al. 2013).
The mine degraded wasteland comprised of stripped areas (59%), open-pit mines
(20%), tailing dams (13%), waste tips (5%), and land affected by mining subsidence
(3%) (Miao and Marrs 2000). A typical mine have limited life, as ore expires the
mining becomes no longer cost-effective and resulted in abandoning as waste sites.
Abandoned mine lands (AMLs) are therefore referred to as “areas or sites of former
mining activity for which no single individual, company, or organization can be held
responsible,” and such sites are also known as “derelict” or “orphan” mines.
Mining is one of the important pathways by which soils get polluted (Ademoroti
1996). Mining has considerable effect on air and water, loss of biodiversity, soil
pollution, and land degradation. Mining also results to clearing of vegetation, reduces
essential nutrients and organic matter of the soil, reduces biological activity, and
decreases productivity of the soil (Pandey and Kumar 1996). The ecological rehabili-
tation of mine spoils is the only approach for the transformation of these ecosystems into
biologically productive ones. Vegetation of mine spoils is often hindered by the lack of
resident microflora which acts as both source and sinks for essential plant nutrients and
is fundamental to the transformation of various nutrients (Ausmus et al. 1976).
There is a great increase in yield per unit land area over past 60 years as a result of
increase in energy inputs in terms of mechanization, irrigation, fertilizer, and pesticide
use. However, these current conventional agricultural practices cannot sustain a healthy
plant-soil system. Soil microorganisms play very important role in reclamation of such
degraded lands and have important influence on soil fertility and plant health. Reme-
diation by biological means and biotechnological innovations is gaining significance
day by day. The importance of microorganisms including nitrogen fixing bacteria in
560 N. Rani et al.
restoring soil fertility and productivity of derelict lands has been stressed by many
researchers (Biro et al. 1994; Rao et al. 2000). There is an urgent need to explore,
isolate, and indentify the indigenous soil microorganisms so that such marginal lands
can also be used for agriculture purpose to meet the demands of food requirements.
Environmental Impacts of Mining
Land degradation due to mining has reached alarming proportions mainly due to
over exploitation and mismanagement of natural resources. One of the consequences
of ever increasing human population, supported by accelerated land degradation, is
lowering of the man-land ratio. Therefore, there is an urgent need to address the
major environmental issues which are the outcome of the mining activities. The
issues include destruction of habitat and biodiversity at the mine site, ecosystem/
habitat/biodiversity protection in adjacent land, landscape/visual impact/loss of land-
use, site stabilization and rehabilitation, mine waste/ tailings disposal, air emissions,
dust, climate change, siltation, and changes in river regimes, effluent discharges and
acid drainage, groundwater alteration or contamination, workplace health and safety,
the impact of metals toxicity, and settlement issues around mines.
Soil environment gets disturbed and contaminated and loses its green cover
owing to mining and related activities exposing more area to erosion. During various
processes in mining activities, nutrients gets leached due to increased erosion rates,
which result in the loss of productivity of the soil as well as the anchorage capacity of
the soil for plants (Chaulya et al. 2000). As water resources get polluted, part or total
of flora and fauna gets lost. The damages go on increasing with accelerated rates and
land is degraded with cumulative effects. Due to lack of proper planning and
negligence of mining regulations, an appreciable amount of environmental degra-
dation and ecological damage to vast area occurs (Dhar and Rolterdem 1993).
The detrimental effects of mining and smelting activities on the environment can
be significant and persistent (Luoma and Rainbow 2008; Lottermoser 2010; Drake
2010). The metals from metalliferous mine wastes get mobilize into the environment
and contaminate sediment and soil that further may adversely affect biota (Peplow and
Edmonds 2006; Angelo et al. 2007). Mechanical and chemical processing of mine
ores generate metalliferous mine wastes, uneconomic material that contains variable
amounts of metallic minerals which can mobilize accumulate metals into the envi-
ronment. The history of extraction of metal goes long back to prehistoric times. It has
been estimated that about 1,150 million tons of heavy metals (Cu, Pb, Co, Zn, Cd, and
Cr) and that of the whole mineral extracted from metal mines, and usually a small
proportion less than 2%, corresponds to the desired valuable metal, while the rest is
discharged as different overburden wastes in areas nearby the mine operation
(Sheoran and Sheoran 2006). Even today, there are no definitive statistics. The
individual mines and quarries manage their waste as amount generated depend
upon the local climatic conditions. Approximately 8,000,000 tons per year (ton/year)
of process residue has been generated by the US mining industry that may contain
hazardous species as well as valuable by-products. These process residues are
produced by smelter off-gas cleaning at approximately 5,500,000 tons/year, and bag

house dust and wastewater treatment at approximately 2,100,000 tons/year (US EPA
1995). According to DEFRA (2007), it was estimated that 96.4 million tons of mining
and quarrying waste was produced in UK in 2004 and one million tons of waste rock
and 950,000 tons of tailings per day, totaling 650 million tons of waste per year has
been generated by Canadian mineral industry alone (SDWF 2011).
After being removed, waste rock is usually stored above ground in large free-
draining piles, which contains acid-generating sulfides, heavy metals, and other
contaminants. This waste rock and the exposed bedrock walls are the primary
sources of pollution due to mining and the effect may be manifest throughout the
life cycle of the mine and even long after mine closure.
Opencast mining operations involve removal of huge quantities of overburden,
dumping and backfilling of the excavated area. These overburden deposits of
waste material containing low-grade ores are represented as mine spoil dumps
(Ekka and Behera 2011). Through technological innovations we can recover
marketable by-products from process residues to generate revenue and reduce
disposal costs for the mining industry. Overburden of stockpiling of mine discards
results into the formation of unsightly landscape and leads to the pollution of
terrestrial and aquatic ecosystems. Gradual increase in such landscapes due to
extensive mining may endanger the ecological balance and productivity of agro-
forest ecosystem (Daily 1995). Further, open-cast coal mining leads to the distur-
bance of geological layers and a new anthropogenic land, that is, substratum, is
created known as deposol is created having no resemblance to the original land.
The characteristics of the landscapes’ appearance have changed due to mining and
this leads to visual pollution. The morphological modifications of terrain occur
due to creation of large scale depressions and the formation of outside overburden
dumps.
Mining operations adversely impact the air quality due to the emissions of
fugitive dusts particulates (dust, diesel, and silica) which leads to the monochromatic
appearance of the mine areas. Coal-mining areas can be seen as black, bauxite, and
iron-ore-rich regions are red, while limestone gives a chalky white hue. Dust results
from blasting, handling, processing, or transporting of soil and rock or can arise from
bare or poorly vegetated areas in combination with air movements. Dust also affects
the agricultural productivity of the area.
Disposal of mine water is a worldwide problem, occurring wherever operating
mines, both underground and opencast. The hydrological pathways get disrupted
and leads to seepage of contaminated leachate into aquifers. Potentially toxic heavy
metals present in the tailings or “spoils” of abandoned mines migrate to the sur-
roundings and cause severe and widespread contamination of farmland soils and
water bodies including the geo-environment disasters (Wong 2003; Beane et al.
2016; Ma et al. 2016).
Mining impacts negatively on agriculture and soils contaminated with heavy
metals are not suitable for agriculture purposes because of the complex catena of
various interactions that occur as waste become part of the ecosystem into which it
is deposited. Mining activities have been reported to have impacts such as
562 N. Rani et al.
oxidation of metal sulfides which induces soil acidification, impeding natural

colonization of vegetation causing soil erosion and degradation of aquatic ecosys-
tem leading to destruction of aquatic life (Lin et al. 2005; Lim et al. 2008; Jian-Min
et al. 2007). If mine wastes are abandoned without implementing a protection
system, the natural spread of wastes by wind, water, and rainfall results in the
contamination of adjacent agricultural soils. Mining operations in semi-arid region
of Brazil is one of the examples of anthropogenic interference to alter most of the
land surface in the region. This activity results in serious problems related to soil
structure, water availability, biological activity, as well as the supply of sulfur,
phosphorus, and nitrogen to plants and hence reduced productivity (Ferreira et al.
2007).
Strategies of Remediation
As a prerequisite for the remediation of areas affected by mining activity, an

understanding of the magnitude and extent of contamination and the environmental
fate and transport of mining-contaminated sediment and soil is required. Three
strategies have been considered in the remediation of contaminated soils: physical,
chemical, and biological. Different physical and chemical technologies have been
proposed for the clean-up of soils contaminated with heavy metals.
Physical
Physical separation technologies include soil washing, vitrification, permeable bar-

rier systems, electrokinetic techniques, mechanical screening, hydrodynamic classi-
fication, gravity concentration, froth flotation, attrition scrubbing, and magnetic or
electrostatic separation.
Chemical
This extraction technologies use different chemical reagents to precipitate metals as

insoluble compounds, or ion exchange, flocculation, and membrane filter processes.
Biological
The biological option, known as natural attenuation, or intrinsic bioremediation,

refers to the use of microorganisms to reduce or remove the effect of harmful
contaminants in the environment and seems an attractive alternative to conventional
physical and chemical techniques. In addition, in the past years, phytoremediation
and rhizoremediation have been developed as a bioremediation technology that

utilizes plants for the removal of metals.
Bioremediation: An Overview
Bioremediation is an option that offers the possibility to destroy or render harmless

various contaminants using natural biological activity. As such, it uses relatively
low-cost, low-technology techniques, which generally have a high public acceptance
and can often be carried out on site. It will not always be suitable, however, as
the range of contaminants on which it is effective is limited, the timescales involved
are relatively long, and the residual contaminant levels achievable may not always be
appropriate. Bioremediation is less expensive, eliminates waste permanently, elim-
inates long-term liability, and can be coupled with physical or chemical treatment
technologies. Furthermore, it is a noninvasive technique, leaving the ecosystem
intact (Vidali 2001).
Microbes are everywhere and often in very large numbers. One can think of
microbes beyond the world in which we all live (i.e., from earth to space). Microbes
are an integral part of biogeochemical cycles which are important for our sustenance.
A large number of these microbes are beneficial to plants, animals, and humans in
one form or the other.
Microbial world, a treasure in itself, if exploited judiciously, can contribute to the
sustainable development. Life originated with microbes and all life is derived from
microbes. Life without higher organisms is possible, but life without microbes is not.
Bioremediation of the degraded land with predetermined end use has the potential to
accomplish it. In the majority of cases, reclamation of degraded land requires the
establishment and maintenance of vegetation on disturbed land. No other medium
can achieve rapid visual integration, surface stabilization, or reduction in air and
water pollution, nor offer a wide variety of land-use possibilities, which can be
achieved at acceptable cost.
Microbe-assisted phytoremediation (MAP) can be proved to be the best environ-
mental practice for reclamation of degraded land. MAP utilizes microbes–soil–plant
interactions for in situ treatment of pollutant contaminated soils, sediments,
and water (Juwarkar and Singh 2010). It can be best applied at sites with relative-
ly shallow contamination of pollutants that are amenable to the processes
such as phytotransformation, rhizosphere bioremediation, phytostabilization,
phytoextraction, and/or rhizofiltration.
Principle of Bioremediation
Bioremediation works on the principle to use the biodegradative process occurring

naturally in the environment to clean the contaminated waste land. Hence, it utilizes
biological methods for cleaning the soil, water, and air, and resulted end products are
564 N. Rani et al.
nontoxic to environment and living organisms. Bioremediation is defined as the

process whereby organic wastes are biologically degraded under controlled condi-
tions to an innocuous state, or to levels below concentration limits established by
regulatory authorities (Mueller et al. 1996). The microorganisms may be indigenous
to a contaminated area or they may be isolated from elsewhere and brought to the
contaminated site. Autochthonous microorganisms present in polluted environments
hold the key to solving most of the challenges associated with biodegradation and
bioremediation of polluting substances as they are genetically adapted to those
conditions (Verma and Jaiswal 2016). Living organisms transformed noxious
waste compounds through their metabolic processes. In nature multiple organisms
are involved in the bio-degradation process, and there is no single bioremediation
technique is available that can serves as a “silver bullet” to re-establish polluted
environments. Bioremediation offers the possibility of degrading, removing, alter-
ing, immobilizing, or otherwise detoxifying various chemicals from the environment
through the action of bacteria, fungi, and plants (Gadd 2001; Morel et al. 2002;
Singh 2006; Willey 2007).
This is environmentally friendly and cost effective technique as compared to
both chemical and physical methods of remediation. For this technique to be
effective, environmental condition should suitable for the microbial growth and
activity and often involves manipulation of environment to allow the microbial
growth and accelerated rate of degradation. This involves the enzymes released by
microorganisms and enzymatic metabolic pathways evolved in nature over very
long periods of time, thus becoming very specific. The combination of such
pathways can make possible the degradation of a wide variety of even hazardous
pollutants.
Bioremediation techniques are typically more economical than traditional
methods such as incineration, and some pollutants can be treated on site, thus
reducing exposure risks for clean-up personnel, or potentially wider exposure as a
result of transportation accidents. Since bioremediation is based on natural atten-
uation, the public considers it more acceptable than other technologies
(Vidali 2001).
Factors Affecting Bioremediation
The bioremediation in nature is a complex process, and this technique required many
performance criteria before applying to the contaminated site. The process of
pollutant removal and rehabilitation depends mainly on the nature of the toxicant
(mining industry, heavy metals, chlorinated compounds, hydrocarbons, nuclear
waste, plastics, and sewage) and relies on biological mechanisms to reduce (degrade,
detoxify, mineralize, or transform) concentration of pollutants to an innocuous state.
Microbial population and environmental factors (oxygen and nutrient concentra-
tions, temperature, pH, and other abiotic factors) determine the success of bioreme-
diation process (Table 1).
Table 1 Physicochemical properties of soil environment required for activities of microorganism

(adapted from Vidali 2001)
Nutrient N P and K for microbial growth C:N:: 10:1;C:P:: 30:1 for bioremediation
Soil moisture 25–28% of water holding capacity
Soil pH 5.5–5.8
Oxygen content Aerobic, minimum air-filled pore space of 10%
Temperature 15–45 C
Heavy metals 2000 ppm
Types of soil Low in clay and silt
Techniques in Bioremediation
There are mainly two types of bioremediation: bioremediation carries on

site or in situ bioremediation and bioremediation carries off site or ex situ
bioremediation.
In Situ Bioremediation
This remediation technique involves inherent metabolic activities of microorganisms

at the site of pollution accompanied by little or no disturbance to soil structure.
Soil excavation is not done under this type of remediation, therefore, minimal site
disruption, minimal dust production, and the possibility of simultaneous treatments
of soil and groundwater in future. It is less expensive and cost effective. The growth
of microorganisms and their ability to bring bioremediation are dependent on the
supply of essential nutrients. In situ bioremediation techniques have been success-
fully used to treat chlorinated solvents, dyes, heavy metals, and hydrocarbons
polluted sites (Folch et al. 2013; Kim et al. 2014; Frascari et al. 2015; Roy et al.
2015). The important environmental condition includes moisture content, the status
of electron acceptor, availability of nutrient, pH, and temperature needed to be
suitable for a successful in situ bioremediation to be achieved (Philp and Atlas
2005). Further in situ bioremediation can be broadly classified into two viz. intrinsic
or natural bioremediation and enhanced or engineered bioremediation.
Intrinsic Bioremediation
This involves biological natural attenuation of contaminants in the environment.
Stimulation of indigenously occurring microbial population is done by feeding them
nutrients and oxygen to increase their metabolic activities. The microorganisms may
be tested at the laboratory for their natural capability of biodegradation and appro-
priately utilized. However, the microorganisms or the site of which the pollutants are
to be removed are not manipulated.
566 N. Rani et al.
Engineered Bioremediation
This involves any type of manipulated or stimulated or enhanced biological reme-
diation of an environment (Hazen 2010). Specific microorganisms are introduced to
the contaminated site to accelerate the degradation process by generating or enhanc-
ing physicochemical conditions (Kumar et al. 2011). The microorganisms may be
genetically modified. But these genetically engineered microorganisms have their
own implication in the imposed stress environmental conditions. Therefore, choos-
ing such bacteria with bioremediation potential without environmental risk is a
crucial step. Accelerated in situ bioremediation is used where it is the desire to
increase the rate of degradation.
Techniques
Bioventing
Bioventing is the most common in situ bioremediation technique that involves
indigenous aerobic microorganisms to degrade the pollutants in soil (subsurface).
Air and nutrients are supplied through wells at the point of contamination or
pollution above water level. The indigenous heterotrophic microorganisms degrade
the pollutants under aerobic condition, and the degraded pollutants are extracted
from the extraction well and safely vented. It employs low air flow rate that provides
the only amount of oxygen needed for bioremediation. The injection of air oxygen-
ates contaminated soil and the contaminating materials/pollutants are biodegraded.
Bioventing has been proved to be very effective in remediating petroleum-
contaminated soil.
Bioaugmentation
When the pollutants are very complex and native soil microorganisms are not
capable of degrading them, additional pregrown specific microbial cultures intrin-
sic or exogenous are added to the contaminated site to enhance the degradation of
unwanted compounds (Tyagi et al. 2011), for example, polychlorobiphenyl, TNT,
polyaromatic hydrocarbon, and pesticides. The seeding of microorganisms aug-
ments metabolic capability of indigenous microbial population and increase the
rate or extent of degradation of the pollutants. A combination of microorganisms
often referred to as “consortium or cocktail” of microorganisms is added to the site
that augments intrinsic bioremediation. In most of the cases, general strains are
added/seeded rather than the special strains of genetically engineered microor-
ganisms (GEMs). The direct use of GEMs may pose several risks and health
hazards.
Biosparging
Biosparging is an in situ bioremediation technique that uses the indigenous
microorganisms to degrade the pollutants in saturated zone. It involves the
injection of air under pressure below the water table to increase groundwater
oxygen concentrations and enhance the rate of biological degradation of contam-
inants by naturally occurring bacteria. In biosparging, oxygen and nutrients
(if needed) are injected into saturated zone to increase the biological activity of
indigenous microorganisms. The effectiveness of biosparging depends on two
major factors namely: soil permeability, which determines pollutant bioavailabil-
ity to microorganisms, and pollutant biodegradability (Philp and Atlas 2005).
Biosparging is most effective at site with medium weight petroleum products such
as diesel, kerosene. Biosparging promotes biodegradation and process is similar
to bioventing. Kao et al. (2008) reported that biosparging of benzene, toluene,
ethylbenzene, and xylene (BTEX)-contaminated aquifer plume and overall
decrease in BTEX reduction (70%) further indicates that biosparging can be
used to remediate BTEX-contaminated groundwater.
Phytoremediation
Phytoremediation relies on the use of green plants and associated microorganisms
interactions in wasteland to mitigate the effects of pollutants elemental or organic.
The plant roots absorb the pollutants and remediate them. Depending upon the type,
there may be several mechanisms viz. accumulating the pollutants in the plant tissue
or extraction, translocation of the pollutants into leaves and volatilization from leaf
surface, metabolism in rhizosphere, and degradation enzymes secreted by microbial
communities and plants. Plant growth rate, adaptability to the prevailing conditions,
resistance to disease and pest, the plant root system (Fibrous and tap root), and
overall time required for achieving desired remediation are some of the important
factors need to be considered before choosing plant for bioremediation (Lee 2013).
The transgenic plants may also be used, for example, Arabidopsis thaliana which
absorbs mercury and has been incorporated with genes coding reductase. Plant
growth-promoting bacteria (PGPR) play an important role in bioremediation process
by enhancing the tolerance of plants to various edaphic conditions (Yancheshmeh
et al. 2011; de-Bashan et al. 2012). The phytoremediation technique is low cost,
environmentally friendly, low installation, and maintenance cost soil structure con-
servation and prevention of soil erosion and leaching of toxicant. Some precious
metal bioaccumulated in the plants can be recovered by the process of phytomining
after the remediation process (Van Aken 2009; Ali et al. 2013). There is overall
improvement of soil fertility and other physic-chemical characteristic of affected
wasteland (Mench et al. 2009).
568 N. Rani et al.
Heavy Metal Sequestration

Metals are essential for life, and they can be harmful to man, animal, plant, and
microorganisms at toxic levels. Soil microbes and plants can be used for remediation
of contaminated soils either directly or by making heavy metals bioavailable in the
rhizosphere of plants. Such plants can accumulate 100 mg g-1 Cd and As; 1000 mg
g-1 Co, Cu, Cr, and Ni; and 10,000 mg g-1 Pb, Mn, and Ni and translocate metals to
harvestable parts. The role of microbial activity in the development and functioning
of soil ecosystem is inevitable, and changes in soil microbial activity may be an
indicator of extremely sensitive changes in the soil health (Pankhurst et al. 1995).
Metal mobility and bioavailability have been shown to be reduced by soil microbes
through biosorption and bioprecipitation (Zhuang et al. 2007; Pajuelo et al. 2011).
These mechanisms also help in immobilization of heavy metals in the soil (Mendez
and Maier 2008).
Microbial activity changes soil physical properties such as soil structure and
biochemical properties such as pH, soil redox state, soil enzymes that influence the
solubility and bioavailability of heavy metals. Some microorganisms like bacteria,
protista, and fungi can degrade heavy metal compounds and transform the end product
into part of their metabolism with the aid of specialized enzymes. During the process,
the heavy metal is either removed or transformed into nontoxic compound.
Microbes have the capability of growing in heavy metal-polluted environment
and also have a significant metal uptake through the process of reduction and
immobilizing toxic metals. Microbial biomass of bacteria, fungi, and yeast has
been used extensively in bioremediation of such waste lands (Shakoori et al.
2004; Zaidi et al. 2011; Morales-Barrera and Cristiani-Urbina 2008). Certain
bacteria and fungi, pseudomonas, achromobacter, flavobacterium, streptomyces,
aspergillus, and arthrobacter form the free living organisms that thrive in the
Table 2 Species of plants and microorganisms commonly used for phytoremediation of heavy
metal contaminated waste land
Plants Ludwigia octovalvis, Aegiceras corniculatum, Spartina maritime, Arundo donax,
Eichhorina crassipes (water hyacinth), Phragmites australis, Plectranthus
amboinicus, Luffa acutangula, Anthracene fluoranthene, Sparganium sp.,
Amaranthus paniculatus, Rizophora mangle, Populusdeltoides x nigra, Arabidopsis
thaliana, Carex pendula, Brassica juncea,Vetiveria zizanioides,Cardaminopsis
halleri,Spartina alterniflora, Medicago sativa, Sorghum halepense, Helianthus
annuus, Pteris cretica, Hordeum vulgare, Avena sativa, Cynodon dactylon.
Algae Chlorella pyrendoidosa, Aspergillus niger, Ascophyllum nodosum,
Bacillus firmus, Chlorella fusca, Oscillatoria anguistissima, Cladophora fascicularis
Hydrodictylon, Oedogonium, and Rhizoclonium species spirogyra
sp., Saccharomyces cerevisiae
Bacteria Pseudomonas veronii, Burkholderia species, Bradyrhizobium sp., Rhizobacteria
sp., Kocuria flava, Serratia marcescens, Pseudomonas aeruginosa, Bacillus cereus,
Halomonas sp., Sporosarcina ginsengisoli, Streptococci, Salmonella, Micrococcus,
and E. coli
Fungi Penicillium canescens, Ganoderma lucidum, Aspergillus versicolor
Aspergillus fumigates, Cladonia rangiformis (lichen), Species of Mucor and Rhizopus
VAM Species of Glomus, Gigaspora, Acaulospora, Scutellospora, and Sclerocystis
rhizosphere. They are known to solubilize phosphate and heavy metals and make
them bioavailable.
Several plant species that accumulate and tolerate heavy metals otherwise known
as hyperaccumulators have been used in the detoxification of metal-polluted soils.
About 400 species of plants including fungi, weeds, and food crops to ornamen-
tals have been identified to hyperaccumulate heavy metals. Heavy metal hyper-
accumulator plants are dominated by Asteraceae, Brassicaceae, Caryophyllaceae,
Cyperaceae, Cunoniaceae, Fabaceae, Flacourtiaceae, Lamiaceae, Poaceae,
Violaceae, and Euphorbiaceae families (Prasad and Freitas 2003). Though most of
them are specific to contaminants, some still have the capability to hyperaccumulate
more than one heavy metal. The plants that accumulate heavy metal beyond
recommended level into their tissue without showing physiological symptoms, for
example, more than 2% of heavy metals (100 mg g-1 Cd and As; 0.01% dry wt.),
(1000 mg g-1 Co, Cu, Cr, Ni; 0.1% dry wt.), (10,000 mg g-1 Pb, Mn and Ni; 1% dry
wt.) and translocate them to the harvestable part (Reeves and Baker 2000; Watanabe
1997) are used for bioremediation of metalliferous soils (Table 2).
Mycoremediation
The importance of AM association in restoration and improvement of revegetation
of disturbed mined lands is well recognized and has been investigated by many
workers (Daft et al. 1975; Reeves et al. 1979; Mukhopadhyay and Maiti 2009).
Vesicular arbuscular (VAM) fungi improve plant growth under low fertility condi-
tions, contribute to the formation of soil structure, and also help plants to become
established in new areas.
570 N. Rani et al.
Schramm (1996) stressed the role of mycorrhizal fungi in the successful estab-
lishment of vegetation on mine overburden as the mycorrhizal fungi help in
mobilizing plant nutrients especially phosphorus and alleviating effects of moisture
stress. Daft and Hacskaylo (1977) reported better establishment of vegetation in
different mine spoils with the use of mycorrhizal fungi. AMF facilitate plant
absorption and uptake of nutrients from the soil, such as phosphorus (Jakobsen
et al. 2001), and can increase plants’ tolerance to toxic elements (Cumming and
Ning 2003; Gattai et al. 2011), plant pathogens (Declerck et al. 2002), saline stress
(Yano-Melo et al. 2003), and erosion (O’Dea 2007). The AMF can also help
stabilize and aggregate soil, increasing the levels of soluble carbon and enzymes
(e.g., urease, acid phosphatase, and β-glucosidase), making them an important
component to improve the growth of young plants under severe climate conditions
(Caravaca et al. 2002).
Arbuscular mycorrhizal fungi help in establishment of many species on
reclaimed mine soils (Waaland and Allen 1987; Hetrick et al. 1994). The symbi-
otic function of these organisms is critical for supplying plants with minerals,
primarily phosphorus, in exchange for organic energy compounds (Gerdemann
1968). AM fungi native to limestone mine spoils may play a critical role in
revegetating the mine spoils in arid areas by improving the water uptake and
transport in plants, enhancing the uptake of various nutrients especially P and the
ability of plants to withstand high temperature. AM fungi improve the biological
productivity of these mine spoils for sustainable plant production and to create a
better ecosystem (Rao and Tak 2002).
VAM fungi adapted in waste dumps can be used for successful reclamation
program. Rios et al. (2013) studied the diversity and activity of arbuscular mycor-
rhizal fungi (AMF) in two selected areas viz. preserved and degraded by limestone
mining with in the semi-arid region of Brazil known as the caatinga (Shrublands).
The results showed AMF species richness and Glomus production remain unaffected
due to mining activity.
Cyanoremediation
The promising bioremediators species of cyanobacteria are Anabena, Nostoc,
Phormidium, Aphanocapsa, Oscillatoria, Lgngbya, Spirulina, Aulosira,
Anasystis. Cyanobacteria metabolize organic compounds through production of
biomolecules (siderophores) that are mainly responsible for absorption of metal
ions into organism. The metal accumulating algal biomass can either be disposed
off or incinerated for metal recovery. Algal detoxification and degradation of
environmental pollutants could help in remediation of polluted aquatic and
terrestrial habitats.
There are several evidences that the disturbed sites may be re-vegetated more
promptly when seedlings of planted species are preinoculated with microbial
inoculants (Adholeya et al. 1997; Bhatia et al. 1998; Anon 2002; Fay et al. 1999;
Franco et al. 1997; Reddell et al. 1999; Sharma et al. 2001). But the uses of beneficial
microorganisms like VAM and Blue Green Algae in the reclamation program has
received less attention and poorly explored. Use of biofertilizer may be helpful in the
development of low cost technology to rehabilitate the mining areas and increase
their productivity. Blue green algae have been reported to act as good soil binder
which improves soil aggregation (Marthe 1972).
Use of beneficial microorganisms like Vesicular arbuscular mycorrhizae (VAM)
Blue Green Algae (BGA), Rhizibium, Azotobactor, Phosphate Solublizing Micro-
organisma (PSM), etc., shows greater potential for reclamation of silica mined areas
(Setiadi 2002). Thus, development of suitable technology package for reclamation of
mined areas through a systematic research program is needed.
Biomolecules
With the development of technologies in restoration of degraded lands, the use of
extracellular biomolecules for the removal of heavy metal is a recent concept.
Extracellular biomolecules are synthesized by microorganisms in response to pol-
lutants and are released into the environment, which accelerate the process of
bioremediation/phytoremediation (Juwarkar et al. 2007). Biosurfactants and
siderophores are such biomolecules which solubilize and/or chelate the pollutants
and can be produced by both plants as well as by microbes.
The biosurfactants are chemical compounds characterized by hydrophobic and
hydrophilic (non-polar and polar) regions in one molecule (amphipathic molecules).
Biosurfactants from bacteria, cyanobacteria, fungi, and yeast are classified into:
glycolipids, lipopeptides, phospholipids, glycoproteins, and polymeric
biosurfactants. Physiologically they play an important role as nutrient storage
molecules and increase the availability of hydrophopic compounds. Efflux of harm-
ful compounds save the microbial cells from toxic substances and help in quorum
sensing through extracellular and intracellular interactions (Fig. 1).
Case Study: Kashlog Mining Area, Darlaghat, Solan, Himachal

Pradesh, India
Himachal Pradesh is known as Dev-bhumi and it is fruit bowl of India. Rapid

industrialization, mining, urbanization, and nonsustainable development have
aggravated the cause of water and soil pollution in the state, which has not only
degraded the quality of water used for irrigation and drinking purposes but also
affected the flora and fauna. The ecology of the system has been degraded a lot
which has also disturbed and imbalanced the natural equilibrium between the
living and nonliving components of the environment. The state now became a hub
of big industries like pharma and cement which has contributed both negative as
well as positive impacts on social and natural environment. In the rural areas, the
farming community is severely suffering due to the cement plants resulting in the
572 N. Rani et al.
( )n1 O ( )n2 O ( )n3 O ( )n4 O
O O O O N COOH
H
O OH
OH
HO
OH Glucolipid from Alcalivorax sp.
CH2OH OH
O
OR
OR
OR O O OH
O CH2OH
O C (CH2)2 COOH Trehalose tetra ester from Arthrobacter sp.
Siderophore:
O
H2N NH O O
O O N Fe
HN N
+ N N O O
O O
O O O
N H
O Fe H
N
NH O O N
H H
O HN O H
O HN O
O O
O O O NH
H H
N H HN Me N
N N N
+ H O Me H H
NH3 O R1 O
Pseudobactin HO Me Ferrichrome
Fig. 1 Chemical Structure of commonly found Biomolecules
change in their cropping systems and shift in their food security mechanism with
rising vulnerability (Vineet et al. 2011). The state has four big cement plants
which include ACC at Barmana, Ambuja Cements Limited at Darlaghat, JP
Cements at Bagha, and CCI at Rajban, which have an aggregate production
capacity of 12.06 million tons.
The total cement and clinker production capacity of various cement plants in the
state would touch 22.37 million tons by 2015 with commissioning of various units in
the state.
The Kashlog Limestone Mine mainly comprises three blocks viz. Western
(Kashlog), Eastern (Mangu), and Central (Pati). The mining area comprises total area
574 N. Rani et al.
of about 488.06 ha falling in Kashlog, Chakru, Serwala Banjan, Pati, Banli, Banog,
Rathoh, Mangu, Chola, Ghamaru, Serjeri, Gyana, Rauri, Sangoi villages of Tehsil Arki
in Solan District of Himachal Pradesh. Geographically, the area falls between Latitudes
31o130 50.500 to 31o150 2800 North and Longitude 76 o550 38.500 to 77o9.500 East with
elevations in the range of 1280–1740 m above Mean Sea Level (MSL).
The topography is rugged and hillocks are barren or comprise euphorbia plants at
majority of places. Some of the patches are characterized by Chill plantation. The
intervening lower horizons are inhabited in the form of small villages or hamlets at
some locations. Overall, the area is characterized by dendritic to subdendritic
drainage pattern (Table 3).
Agriculture is chief occupation of people in Himachal Pradesh, and it is the main
source of income as well as employment. With growing demand for safe and healthy
food, long-term sustainability and concern on environmental pollution associated
with indiscriminate use of chemical in the agriculture, organic farming using
Table 3 Flora of Kashlog Mining Area

Angiosperm and Gymnosperm plants grow in the study area:
Plant Colebrookia appositifolia, Sonchus asper, Catharanthus roseus, Mallotus
species philippinensis, Oxalis corniculata, Sida rhombifolia, Woodfordia fruiticosa,
Solanum surattense, Parthenium hysterophorus, Rubus niveus, Justicia athatoda,
Berberis aristata, Karsica opaca, Aspargus sp., Bidens pilosa, Rumex sp., Toona
ciliate, Ficus hispida, Punica granatum, Citrus lemon, Zizipus jujube, Ficus virels,
Morus alba, Pinus roxburgii, Grewia oppositifolia, Syzygium cumini
biofertilizer has emerged as an important priority area. Biofertilizers play a very

significant role in improving soil fertility by fixing atmospheric nitrogen, both in
association with plant roots and without it, solubilize insoluble soil phosphates and
produce plant growth substances in the soil. Application of organic manures partic-
ularly biofertilizers is the only option to improve the soil organic carbon for
sustenance of soil quality and future agricultural productivity.
Lack of region specific strains is one of the major constraints in popularizing the
biofertilizers as these are not only crop specific but soil and region specific too.
Therefore, in the present study, the indigenous strains of Blue Green algae and
Mycorrhizal has been isolated and selected strains having higher reclamatory poten-
tial would be used for further restoration of degraded lands.
Soil Sampling
The soil samples were collected from six villages viz. adjoining Mining site of
Chakhru, agricultural fields of Chakhru, Kashlog, Chandi, Gyana, and Kararaghat
village of Kashlog mining area, Darlaghat, Distric Solan, Himachal Pradesh.
Rhizospheric soils samples were collected from different depths after removing the
top soil, that is, 10 cm, 15 cm, 20 cm below the surface. The samples were collected and
transferred to laboratory in a good quality, air tight, and clean plastic bags for analysis.
Isolation of VAM and Cyanobacteria
Isolation of VAM spores, wet sieving, and decanting technique (Gerdemann and
Nicolson 1963) was followed. Spores were identified according to, size, shape, wall
characteristics. (Schench and Prez 1988). Cyanobacterial strains were isolated from
fresh soils using serial dilution (102) following standard culturing and purification
techniques (Kaushik 1987) using N-free BG-11 medium.
A total of 13 species of VAM fungal spores belonging to 6 genera (Acaulospora,
Claroideoglomus, Dentisculata, Glomus, Scutellospora, Gigaspora) were isolated
from rhizospheric soil of Triticum aestivum. The fungal spores isolated were
Acaulospora longula, Acaulospora scrobiculata, Acaulospora denticulate,
Claroideoglomus etunicatum, Gigaspora gigantea, Glomus aggregatum, Glomus
ambisporium, Glomus clarum, Glomus occultum, Glomus rubiforme, Glomus
spercum, Scutellospora minuta, and Dentisculata nigerita (Fig. 2). Glomus was
found most dominant genus with six species in the present investigation.
Eight species of cyanobacteria belonging to two different orders viz.
Stigonematales (1) and Nostocales (7) of class Cyanophyceae were isolated and
purified. 7 isolates belongs to 3 different genera, that is, Anabaena (1 sp.), Nostoc
(5 species), Cylindrospermum(1 sp.). The order Stigonematales represented by
genus Hapalosiphon (1sp.). The genus Nostoc was found to be most dominant in
this area with five isolates (Fig. 3).
576 N. Rani et al.
Fig. 2 VAM spores from Kashlog Cement Mining area, Darlaghat, Himachal Pradesh:
Acaulospora longula (a) Acaulospora scrobiculata (b) Acaulospora denticulata (c)
Claroideoglomus etunicatum (d), Gigaspora gigantean (e), Glomus aggregatum (f), Glomus
ambisporium (g), Glomus clarum (h), Glomus occultum (i), Glomus rubiforme (j) Glomus
spercum (k), Scutellospora minuta (l), Dentisculata nigerita (m) (From Authors published Data;
Rani and Sagar 2017)
Conclusions
Microorganisms are the integral part of the soil and act as a self-regenerating source
of nutrients. These “Bioinoculants or Biofertilizers” are environment friendly and
economically viable and play a critical role in improving and sustaining soil health
and crop yields in a long-term soil management. Use of beneficial microorganisms
like vesicular arbuscular mycorrhizae (VAM), blue green algae (BGA), Rhizobium,
Azotobactor, Phosphate solublizing microorganism (PSM), etc., shows greater
Fig. 3 Cyanobacterial isolates from Kashlog Cement Mining area, Darlaghat, Himachal Pradesh:
Anabaena sp. (a) Cylindrospermum sp. (b) Hipalosiphon sp. (c) Nostoc sp. (d-h) (From Authors
published Data; Rani and Sagar 2017)
578 N. Rani et al.
potential for reclamation. Thus, development of suitable technology package for

restoration of mined areas through a systematic research program is needed.
Soil microorganisms perform many important functions such as maintaining soil
structure, cycling of nutrients, helping in affecting soil fertility, promoting plant
growth along with suppressing various plant diseases. Collectively, biodiversity is
the main engineers that perform a key role in governing wide range of ecological
processes if correctly assembled in time and space. As correctly said that microor-
ganisms can candidly live without us, however, we cannot survive without the
universal catalysis and ecological transformations these provide.
Acknowledgments Dr. Nisha Rani is thankful to UGC, New Delhi, India for financial assistance
in the form of UGC- PDF for Women fellowship.
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Soil Pollution and Remediation
23
Nataša Stojić, Snežana Štrbac, and Dunja Prokić
Contents
Inorganic Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
Arsenic (As) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
Cadmium (Cd) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
Chromium (Cr) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
Copper (Cu) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
Mercury (Hg) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
Lead (Pb) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
Bioavailability of Heavy Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
Enrichment Factors (EFs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
Contamination Factor (CF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
Geoaccumulation Index (Igeo) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
Potential Ecological Risk Load Index (PERI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 592
Human Health Risk Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 592
Organic Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
Intentionally POPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
Unintentionally POPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599
Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
Soil Pollution Caused by the Disposal of Solid Waste to Unsanitary Landfills . . . . . . . . . . . . 604
The Criteria for the Classification of Contaminated Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
The Criteria for the Remediation and the Remediation of Contaminated Sites . . . . . . . . . . . . 609
The Process of Risk Management in the Context of the Remediation of
Contaminated Sites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 609
Methods and Techniques of Performing Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 611
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
N. Stojić (*) · S. Štrbac · D. Prokić

Faculty of environmental protection, University Educons, Sremska Kamenica, Serbia
e-mail: natasa.stojic@educons.edu.rs

https://doi.org/10.1007/978-3-319-73645-7_81
584 N. Stojić et al.
Abstract
The management of solid waste is one of the challenges facing any urban area in
the world. Although in developing countries the quantity of solid waste generated
in urban areas is low compared to industrialized countries, the municipal solid
waste management (MSWM) still remains inadequate. A typical solid waste
management system in a developing country displays an array of problems,
including low collection coverage and irregular collection services, crude open
dumping and burning without air and water pollution control, etc. This segment
of the research deals with the issue of remediation of contaminated sites, with
special emphasis on areas contaminated with pollutants originating from the
disposal of solid waste streams. The need for implementation of the research
comes from the results of qualitative and quantitative analysis of organic and
inorganic pollutants in the soil conducted by our team.
Soil conservation is fundamental for the sustainable development and preser-
vation of ecosystems and biodiversity. Heavy metal concentration in the soil
dependent on the parent material on which it is formed, the formation processes,
and the composition and proportion of the components of the solid phase. This
concentration may be affected by several anthropic activities such as: irrigation,
fertilizer and chemical applications, and industrial or urban sewage incorporation.
The soil type, topography, geology, and the erosive processes influence the
concentration and distribution of heavy metals in the environment, including
their bioavailability. The main objective of this part of study was to assess the
origin of the heavy metals in the soil.
Persistent organic pollutants (POPs) are another group of pollutants in the soil.
Sources of pollution from POPs include the incorrect use and/or disposal of
agrochemicals and industrial chemicals and improper burning. There are eight
initial POPs pesticides (aldrin, chlordane, DDT, dieldrin, endrin, heptachlor,
hexachlorobenzene, mirex, and toxaphene) and five new POPs chemicals which
may be categorized as pesticides (alpha hexachlorocyclohexane, beta hexa-
chlorocyclohexane, chlordecone, lindane, and pentachlorobenzene). Because of
their widespread distribution and their potential toxicity to organisms, these
compounds are of environmental significance. In present study were also
included some POPs chemicals originating from industry such as polychlorinated
biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and polyaromatic
hydrocarbons (PAHs). Third part of the study covers methods for soil sampling,
sample preparation, and instrumental analysis of agrochemical and
industrial POPs.
Keywords
Arsenic · Bioavailability of metals · Cadmium · Chromium · Contaminated sites ·
Contamination factor · Copper · Dioxins · Enrichment factor · Environment ·
Furans · Geoaccumulation index · Heavy metals · Inorganic pollutants ·
Landfills · Lead · Mercury · Nickel · Organic pollutants · PAHs · PBDEs · PCBs ·
23 Soil Pollution and Remediation 585
Pesticides · Pollutants · POPs · Remediation · Risk assessment · Soil

contamination · Soil pollution · Waste disposal · Waste management · Waste · Zinc
Inorganic Pollutants
The soil is a complex heterogeneous medium comprising mineral and organic

solids, aqueous and gaseous components. The minerals present are usually chem-
ically decomposing rock fragments and secondary minerals such as phyllo-silicates
or clay minerals, oxides of Fe, Al, and Mn and sometimes carbonates (usually
CaCO3). The organic matter comprises living organisms (mesofauna and microor-
ganisms), dead plant material, and colloidal humus formed by the action of
microorganisms on plant litter (Alloway 1995). Metals are natural constituents of
the soil, but their presence has exponentially grown since the beginning of the
industrial revolution (Kabata-Pendias and Pendias 1989). Several heavy metals,
such as cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), lead (Pb),
nickel (Ni), zinc (Zn), and the metalloid arsenic (As), are widely used by industries,
agriculture and consequently released into the environment (Štrbac et al. 2014a;
Cristaldi et al. 2017).
Arsenic (As)
Arsenic is the 20th most ubiquitous element in the environment with an estimated
concentration in the Earth’s crust ranging from 1.5–3 mg kg1. Concentrations of As
in the environment increases through both point and diffuse sources that may be
natural (volcanic emissions, rock weathering, and discharge from hot springs) or
anthropogenic activities (smelting, and the use of arsenicals as pesticides and herbi-
cides, mining processes, and wood preservatives). The background concentration of
As in the soil ranges from 0.1 to 40 mg kg1 and significantly differs among
geographic regions. Table 1 summarizes As contamination in soil in different parts
of the world (Farooq et al. 2016).
Table 1 Selected Country/Region Location As concentration (mg kg1)
references of As
Bangladesh Tala Upazilla 3.2–51.8
concentrations in soil
in different parts of India Central India 16–417
the world (Farooq et al. Pakistan Punjab 7–35
2016) Taiwan Taipei 4.71–315
China Inner 154–238
USA Hawaii 15–950
Brazil Minas Gerais 200–860
Chile Chiu-Chiu 41.12–65.72
Mexico Durango 55–221.1
Spain Salamanca 70–5330
Cadmium (Cd)
Cadmium is regarded as one of the most toxic trace elements in the environment. The
average concentration of Cd in the lithosphere is 0.098 mg kg1. It is a rarer element
than Hg and about 1/700 as abundant as Zn (whose crustal abundance averages
70 mg kg1). The ranges and mean concentrations of Cd for some common igneous,
sedimentary, and metamorphic rocks are presented in Table 2.
Soils may be contaminated with Cd by fallout from aerial sources, by application
of waters, fertilizers, or pesticides which contain cadmium, or by the discharge of
Cd-containing waste materials from industrial, metallurgical, or urban activities.
Amounts of indigenous Cd in cultivated and noncultivated soils are determined by
the quantities of Cd in the parent materials together with amounts added through
atmospheric deposition, fertilizers, pesticides, and irrigation water but minus
amounts removed by leaching, erosion, and in harvested crops (Page et al. 1987).
Chromium (Cr)
Chromium is found in all phases of the environment, including air, water, and soil.
The ranges and mean concentrations of Cr in the environment are presented in
Table 3. Naturally occurring in soil, Cr ranges from 10 to 50 mg kg1 depending
Table 2 Abundance Rock type Cd content (mg kg1)

of Cd in common rocks
Igneous
(Page et al. 1987)
Granite 0.001–0.60
Basalt 0.006–0.60
Ultramafic 0.001–0.03
Metamorphic
Gneisses 0.007–0.26
Schist 0.005–0.87
Eclogite 0.04–0.26
Sedimentary
Limestone 0.001–0.50
Sandstone 0.01–0.41
Shale, clay 0.02–11.0
Red clay
Organic mud
Deep ocean sediments 0.005–17
Oceanic manganese oxides <3.0–21
Phosphorites <10–500
Recent sediments
Lake sediments 0.02–6.2
Stream sediments 0.03–0.40
Table 3 Chromium Sample type Concentrations (mg kg1)

concentrations in the
Natural soil 5–1000
environment (Shanker
et al. 2005) 5–3000
5–1500
30–300
Serpentine soils 634–125,000
World soils 200 (mean)
100–300
10–150 (mean 40)
US soils 25–85 (mean 37)
57 (mean)
Canadian soils 100–5000 (mean 43)
Japanese soils 87 (mean)
Swedish soils 74 (mean)
Sediments 0–31,000
on the parental material. In ultramafic soils (serpentine), it can reach up to 125 mg

kg1. Cr and its compounds have multifarious industrial uses. They are extensively
employed in leather processing and finishing, in the production of refractory steel,
drilling muds, electroplating cleaning agents, catalytic manufacture, and in the
production of chromic acid and specialty chemicals. These anthropogenic activities
have led to the widespread contamination that Cr shows in the environment and have
increased its bioavailability and biomobility (Shanker et al. 2005).
Copper (Cu)
Copper is a reddish metal that occurs naturally in rock, soil, water, sediment, and, at
low levels, air. Its average concentration in the earth’s crust is about 50 mg kg1. Cu
also occurs naturally in all plants and animals. It is an essential element for all known
living organisms including humans and other animals at low levels of intake. Cu can
enter the environment through releases from the mining of copper and other metals
and from factories that make or use Cu metal or Cu compounds. Copper can also
enter the environment through waste dumps, domestic waste water, combustion of
fossil fuels and wastes, wood production, phosphate fertilizer production, and
natural sources. Soil generally contains between 2 and 250 mg kg1 Cu, although
concentrations close to 17,000 mg kg1 have been found near copper and brass
production facilities (ATSDR 2004).
Mercury (Hg)
In soils, mercury occurs mainly in the Hg0 and Hg2+ valence states. The average
terrestrial concentration of mercury in the Canadian environment is in the range of
0.01–0.4 mg kg1, except in areas of ore deposits, spills, landfills, and accidents at
metal-processing plants. In Ontario, agricultural soils observed mercury concentra-
tions ranging from 0.01 to 1.14 mg kg1, with a mean of 0.11 mg kg1. In surface
soil samples from areas not impacted by local point sources of pollution throughout
Ontario, the 98th percentiles of mercury concentration measurements are 0.13 and
0.18 mg kg1 for rural parkland and old urban parkland soils, respectively. In
Alberta soils, background mercury levels range from 0.01 to 0.135 mg kg1.
Elevated mercury levels are common in British Columbia due to the cinnabar
deposits. High soil mercury levels are also reported in Quebec and Ontario near
areas of known gold, copper, or zinc mineralization (CCME 1997).
Lead (Pb)
Lead occurs naturally in the soil in concentrations ranging from 10 to 50 mg kg1.

Low-level lead contamination is common in urban areas because of the widespread
use of lead in man-made products and industrial processes. Airborne lead emissions
from local industries may have settled in area yards over many decades. There are
many sources of lead exposure. The most common are deteriorated paint in older
housing, and dust and soil that are contaminated with lead from old paint, drinking
contaminated food and water, and past emissions of leaded gasoline. Some states have
stricter standards, but the Environmental Protection Agency allows concentrations of
400 mg kg1 Pb in soil where children play and 1200 mg kg1 in other areas of bare
soil. The EPA doesn’t have specific standards for a safe level of soil lead for vegetable
gardening, but various organizations and researchers have attempted to come up with
a number – somewhere between 300 and 600 mg kg1 (Finster et al. 2003).
Nickel
Naturally, nickel occurs widely in the environment, being released through both
natural and anthropogenic sources but seldom in its elemental form. Ni natural
source to the environment include forest fires and vegetation, volcanic emissions
and wind – blown dust, while, the anthropogenic activities resulted in atmospheric
accumulation of Ni from combustion of coal, diesel oil, and fuel oil, the incineration
of waste and sludge, as well as from miscellaneous sources. Application of some
phosphate fertilizers are also important sources of Ni into environment as pollutants.
Ni is the 24th most abundant metal in the Earth’s crust and 5th most abundant
element by weight after Fe, O, Mg, and Si, constituting about 3% of the earth
composition. Its status in soils is highly dependent on the Ni concentration of the
parent rocks, but in surface soils, its content is also a reflection of soil forming
processes and pollution. The lowest contents are found in sedimentary rocks that
comprise of clays, limestones, sandstones, and shales, while the highest concentra-
tions exist in basic igneous rocks. Ni content in soils varied widely and has been
estimated to range from 3 to 1000 mg kg1; for the world soils, the brand range is
Table 4 Bioavailability Jurisdiction Guideline (mg kg1)

and application to
Australia 350–2000
differing land uses
(American Galvanizers Canada 360
Association) European union 70–150
United States 120–160
Average natural (background) level 50–70
between 0.2 and 450 mg kg1, while the grand mean is calculated to be 22 mg kg1.
The natural Ni content in the Earth’s crust is 86 mg kg1. Values representing the
contamination level of nickel in rural soils of the world for various countries have
been reported: Australia (60 mg kg1), Canada (150 mg kg1), China (20 mg kg1),
France (50 mg kg1), Germany (200 mg kg1), Japan (100 mg kg1), the Nether-
lands (210 mg kg1), South Africa (15 mg kg1), the United Kingdom (60 mg
kg1), and the United States of America (420 mg kg1) (Iyaka 2011).
Zinc
In the soil, zinc is bound to the soil complex (clay, organic material, etc.) depending on
different physicochemical soil factors such as pH and organic matter content and other
factors like cation exchange capacity, redox potential, mineral composition, and
moisture content. These factors determine the solubility of zinc contained in soil and
consequently, its bioavailability for uptake by organisms. Soil quality guidelines for
national/regional jurisdictions vary in their consideration of bioavailability and appli-
cation to differing land uses (Table 4). Australia and the European Union both
comprehensively consider geochemical properties when interpreting effects data for
zinc and deriving guidelines. Currently, the US Environmental Protection Agency
(USEPA) does not consider such factors and has for now set a conservative/worst case
Ecological Soil Screening Level of 120–160 mg kg1. However, recent efforts among
scientists and regulators to incorporate the methods applied by Australia and the EU
have resulted in newly published methodology for use by the USEPA. The proposed
approach will account for critical confounding factors in soils risk assessment –
background, bioavailability, and land use (American Galvanizers Association).
Bioavailability of Heavy Metals
Changes that control concentration and free metal activity of heavy metals in soil
affect their bioavailability. Soil properties that control the mobility of metals include
pH, redox potential, organic matter content, and soil mineralogy (Liphadzi and
Kirkham 2005). Soil pH is the major factor affecting metal availability. Most
heavy metals are soluble and mobile in acid soils. High pH increases the complex-
ation of metals by functional groups of organic matter and oxides, which results in
the reduction of metal concentration in the soil solution (Liphadzi and Kirkham
2005). Metals with more than one oxidation state are generally less soluble in their
higher oxidation states. Most heavy metals are strongly immobilized by reducing
conditions (Liphadzi and Kirkham 2005).
Bioavailability of metals decreases in soil with high amounts of organic
matter, clay, or oxides. The quantities of organic matter, clay, and oxides control
metal speciation, movement, and bioavailability, because the metal cations react
with those components that have high specific areas and cation exchange capac-
ity. The complexation of metals by organic matter reduces the activities of metals
in solution. Some heavy metals may be bound to humic substances in the inner-
sphere complexes and become nonexchangeable (Liphadzi and Kirkham 2005).
The heavy metals present in soil can be found in different forms: as free metal
ions; as a soluble metal complexes; associated to soil organic matter; as oxides,
hydroxides, and carbonates; incorporated into silicate minerals structure (Allo-
way 1995).
Before taking effective measures to protect soil quality, it is very necessary to
identify heavy metal inputs. It is generally considered that natural and human
activities are the two major origins of heavy metals. Natural sources of soil heavy
metals are mainly controlled by the geological parent material. In addition, anthro-
pogenic inputs of soil heavy metals are attributed to metalliferous industries, mining,
vehicle exhaust, agricultural practices, coal combustion, and atmospheric deposition.
Different methods have been widely used to assess the contamination of heavy
metals and metalloids in soil such as enrichment factor (EF), contamination factor
(CF), and geoaccumulation index (Igeo) (Štrbac 2016). To evaluate the combined risk
of numerous heavy metals and metalloids in soil, the pollution load index (PLI) and
potential ecological risk index (PERI) have also been developed (Štrbac et al.
2014b).
Enrichment Factors (EFs)
Enrichment factor (EF) is an appropriate methodology which helps to differentiate a

metal source of anthropogenic origin from those occurring naturally in the environ-
ment. Enrichment factor is calculated by normalizing the given metals’ concentra-
tion in soils to the percentage of Al. The EF is calculated according to the following
equation:
EF ¼ ðCM =CAL Þsample =ðCM =CAL Þbackground
where (CM/CAl) sample is the ratio of concentration of heavy metals (CM) to that
of aluminum (CAl) in soil sample and (CM/CAl) background is the same reference
ratio in the preindustrial sample. Generally, an EF value of about 1 suggests that a
given metal may originate entirely from crustal source or natural processes of
weathering. Samples having enrichment factor >1.5 is considered indicative of

human influence and arbitrarily, an EF of 1.5–3, 3–5, 5–10, and >10 is considered
as evidence of minor, moderate, severe, and very severe contamination, respec-
tively (Islam et al. 2017).
Contamination Factor (CF)
CF is the ratio obtained by dividing the concentration of each metal in soil by the
baseline or background value (heavy metals and metalloids in the preindustrial soil
sample of the study area). Contamination factor can be calculated based on the
equation:
CFi ¼ Cmetal =Cbackground
where Cmetal is concentration of the concerned heavy metal in soil sample and
Cbackground is the concentration in unpolluted soil (background value). The contam-
ination levels may be classified based on their intensities on a scale ranging from 1 to
6: low degree (Cif < 1), moderate degree (1 Cif < 3), considerable degree
(3 Cif < 6), and very high degree (Cif 6) (Islam et al. 2017).
Geoaccumulation Index (Igeo)
To quantify the degree of heavy metals pollution, the geoaccumulation index (Igeo)
was calculated as follows (Rastegari Mehr et al. 2017):
Igeo ¼ Log2 ½Cn =1:5Bn
where Cn is concentration of examined metal in soil, Bn is geochemical background

value of given metal, and factor 1.5 is used to account the possible variations in the
background values. Igeo < 0 indicates practically unpolluted, 0–1 is unpolluted to
moderately polluted, 1–2 is moderately polluted, 2–3 is moderately to strongly
polluted, 3–4 is strongly polluted, 4–5 is strongly to extremely polluted, and >5
shows extremely polluted (Rastegari Mehr et al. 2017).
The mutual pollution effect at different stations by different metals can be
calculated using pollution load index. PLI is the geometric mean of the CF values
for the n metals:
p ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
PLI ¼ n
CF1 CF2 . . . CFn
• A PLI value close to 1 indicates heavy metals load near the background level,
while values >1 indicate pollution (Rastegari Mehr et al. 2017).
Potential Ecological Risk Load Index (PERI)
Potential ecological risk load index (PERI) is used to assess the degree of metal
contamination in soils. The equations for PERI are as follows.
Ci f ¼ C1 =Ci n ,
Cd ¼ Σn i¼1 Ci f ,
Ei r ¼ Ti r x Ci f ,
PER ¼ Σn i¼1 Ei r
where Cif is the contamination factor of a single metal, Ci is the content of metal in
samples, and Cin is the background value of the heavy metal. The background values
(preindustrial samples of the study area) of Cr, Ni, Cu, As, Cd, and Pb in soils were
29, 32, 27, 6.5, 0.82, and 23 mg kg1, respectively. The sum of contamination factor
(Cif) for all metals represents the integrated pollution degree (Cd). Eir is the potential
ecological risk index and Tir is the biological toxic factor of an individual metal. The
toxic-response factors for Cr, Ni, Cu, As, Cd, and Pb were 2, 6, 5, 10, 30, and
5, respectively (Islam et al. 2017). PER is the comprehensive potential ecological
risk index, the sum of Eir.
Human Health Risk Assessment
Human health risk assessment of metals in soils is related to hazard discrimination,

exposure evaluation, and risk characterization. In consideration of potential toxicity
and carcinogenicity of most elements, carcinogenic and noncarcinogenic effects of
metals can be studied. Three exposure ways of metals to human body can be
considered: direct oral ingestion of soil particles (ADDing), dermal absorption of
elements in soils adhered to exposed skin (ADDdermal), and inhalation of
resuspended soil particulates by nose or mouth (ADDinh). This methodology was
developed by the United States Environmental Protection Agency for health risk
assessment (USEPA 1989). The population is divided into two parts: adults and
children. One population group that could potentially be more highly exposed to
inhalation exposures at a site is children. The definition and reference values for all
parameters are listed in Table 5. The equations for exposure dose are as follows:
Direct oral ingestion of soil particles (ADDing):

ADDing mg kg1 d1 ¼ C mg kg1 ððIngR EF EDÞ=ðBW ATÞÞ
106
Dermal absorption of elements in soils adhered to exposed skin (ADDdermal):

Table 5 Definition and reference value of some parameters for health risk assessment of metal in
soils (Sun et al. 2017)
Symbol (units) Parameter Value
IngR (mg day1) Soil ingestion rate 200 (children); 100 (adults)
InhR (mg day1) Soil inhalation rate 7.6 (children); 20 (adults)
EF (d a1) Exposure frequency 180
ED (a) Exposure duration 6 year (children); 24 year (adults)
BW (kg) Body weight 15 (children); 70 (adults)
SA (cm2) Exposed skin surface 1150 (children); 2145 (adults)
area
SL mg Adherence factor AF 0.2 (children); 0.07 (adults)
cm2 day1)
ABS (unitless) Dermal absorption 0.001
factor
AT (day) Average time ED 365 (noncarcinogenic); 70 365
(carcinogenic)
PEF (m3 kg1) Emission factor 1.36 109

ADDinh mg kg1 d1 ¼ C mg kg1
ððIngR EF EDÞ=ðPEF AT BWÞÞ
Inhalation of resuspended soil particulates by nose or mouth (ADDinh):

ADDdermal mg kg1 d1 ¼ C mg kg1
ððSA SL ABS EF EDÞ=ðBW ATÞÞ
106
where ADDing, ADDdermal, and ADDinh are the average daily intake from soil
ingestion, dermal, and inhalation absorption, respectively (mg kg1 d1) and C is
the concentration of metal in soil (mg kg1).
The doses calculated for each element and exposure pathway are subsequently
divided by the toxicity threshold value which is referred to as the reference dose (RfD,
mg kg1 d1) of a specific chemical to yield a noncarcinogenic hazard quotient (HQ),
whereas for carcinogens, the dose is multiplied by the corresponding slope factor
(SF) to produce a level of cancer risk (Sun et al. 2017). To assess the overall potential
for noncarcinogenic effects posed by all exposure pathways, a hazard index
(HI) which is the total noncarcinogenic risk of exposure to a variety of pollutants
has been employed as described by Sun et al. (2017). If HQ < 1 or HI < 1, the
exposed individual is unlikely to experience obvious adverse health effect. On the
contrary, if HQ > 1 or HI > 1, there is a chance that noncarcinogenic effect may occur
with a probability which tends to increase as HI increases (Sun et al. 2017).
X X
HI ¼ HQ ¼ ADDi =RfDi
Generally, carcinogenic risk is regarded as the probability of an individual

developing any type of cancer in the whole lifetime due to exposure to carcinogenic
hazards (Sun et al. 2017). Similarly, the aggregate carcinogenic risk (Risk) is
calculated by summing the individual cancer risk across all exposure pathways:
Risk ¼ ADD SF
Organic Pollutants
Persistent organic pollutants (POPs) are, by definition, organic compounds highly

resistant to photolytic, biological, and chemical degradation. These compounds are
also moderately volatile, allowing their long-distances atmospheric transport. POPs
compounds are very poorly dissolved in water, and very good in fats, and easily pass
through phospholipid structures of biological membranes, after which they are
deposited in fatty tissue and other high lipid-containing tissues. All these properties
ensure the widespread distribution of these compounds in the environment, even in
those regions where they have never been used. Because of this, POPs chemicals are
characterized as a ubiquitous class of compounds.
Although there are natural sources of organochlorine compounds, most POPs
chemicals originate from anthropogenic sources, which are related to the production,
application, and disposal of these chemicals.
The general population is most often exposed to POPs chemicals through food.
Often these substances are present in the workplace and in the environment. Expo-
sure to POPs compounds can cause harmful effects on human health. These effects
most often include neurological disorders, disorders of liver function, reproductive
system, behavioral, immune, and endocrine disorders, as well as carcinogenic
effects.
Due to the potential hazard posed by POPs properties, these days, special
attention is paid to the system of control and management of toxic substances and
waste. There are international conventions, regulations, and protocols, which regu-
late certain details related directly or indirectly to POPs chemicals, that have been
adopted and applied. One of them is Stockholm Convention (Stockholm Convention
2001) for POPs adopted in 2001 in Stockholm. According to the Convention, there
are 12 initial and 16 new POPs compounds which can be placed in two categories:
intentionally and unintentionally POPs (Fig. 1).
Intentionally POPs
Group of intentionally POPs includes agrochemicals like organochlorine pesticides

(OCP) and industrial chemicals like PCBs, some polybrominated diphenyl ethers
(PBDE) etc.
POPs
Intentionally Unintentionally
Industrial
Agrochemicals PAHs Furans Dioxins
chemicals
Fig. 1 POPs categories
Agrochemicals
Pesticides
POPs pesticides originate almost entirely from anthropogenic sources and are
associated largely with the manufacture, use, and disposition of certain organic
chemicals. Despite the efforts to use biodegradable and less persistent pesticides in
developing countries, organochlorine pesticides like HCH, DDT, heptachlor, and
chlordane are still being used. Due to their long-distance transport capability, this is
not only a problem of countries that produce and use them but also is a problem for
developed countries and for areas where they have never been used such as the
Antarctic (Kang et al. 2012). The presence of pesticides on the Antarctic has been
confirmed already 50 years ago. A group of scientists found residues of pesticides in
vertebrates: fish species, Adelie penguins, Weddell seals, and Skuas (George and
Frear 1966). Despite the prohibition of use, some OCPs are still present on these
nontarget areas. As part of the 2007–2008 International Trans Antarctic Scientific
Expedition (ITASE) program, surface snow samples were obtained from the coastal
areas to the interior regions of East Antarctica. The samples were analyzed for OCPs
and trace inorganic elements. Of the 22 OCPs, α-hexachlorocyclohexane (HCH),
γ-HCH, and hexachlorobenzene (HCB) were frequently detected in the snow with
concentration ranges of 17.5–83.2, 33–137, and ND–182 pg L1, respectively.
These results indicate that the OCPs were subjected to long-range atmospheric
transport and were deposited in the surface snow.
Hexachlorocyclohexane (HCH) is one of the polyhalogenated organic com-
pounds: α-HCH, β-HCH, or γ-HCH (lindane). Contrary to lindane, alpha-HCH and
beta-HCH are not intentionally produced. They are produced as a part of technical
HCH which is used as an insecticide or as an intermediate chemical in the
manufacturing of lindane. Linadane was used as an insecticide on fruit, vegetables,
and forest crops, and animals and animal premises. Although technical-grade HCH
is no longer used as an insecticide in many countries, α-, β-, and γ-HCH have been
found in the soil and surface water at hazardous waste sites because they persist in
the environment. In humans, breathing toxic amounts of γ-HCH and/or α-, β-HCH
can result in blood disorders, dizziness, headaches, and possible changes in the
levels of sex hormones in the blood (ATSDR 2005a). HCH (all isomers) as possibly
carcinogenic to humans. The EPA has determined that there is suggestive evidence
that lindane (γ-HCH) is carcinogenic, but the evidence is not sufficient to assess its
human carcinogenic potential. The EPA has additionally classified technical HCH
and α-HCH as probable human carcinogens, β-HCH as a possible human carcinogen
(US EPA 2005).
Chlordane is a more highly chlorinated analogue of heptachlor. The technical
mixture contains chlordane, heptachlor, nonachlor, and related componds. Chlor-
dane is a man-made chemical and popular pesticide that was used in the United
States from 1948 to 1988. Due to concerns about environmental damage and human
health risks, the US Environmental Protection Agency banned the use of chlordane
in 1983, except for controlling termites (US EPA 1997). It was banned for that use,
and all uses, in 1988 but still its effect is felt across the world. Chlordane is readily
absorbed in both animals and man through the skin, ingestion, and probably also
inhalation. Some accumulation occurs in the body on repeated exposure – mainly in
adipose tissue. Elimination from the body is fairly slow. Food is the major source of
exposure of the general population to chlordane. Significant exposure to chlordane
can occur in buildings where chlordane has been used for termite or other insect
control. Chlordane is rapidly metabolized in organisms into oxychlordane and
γ-chlordane or into impurities such as trans-nonachlor or cis-nonachlor. These are
metabolic products that persist in the tissue of fish (Joseph et al. 1987), birds (Fiska
et al. 2001), and mammals and that are found in breast milk. In the 1980s, when there
was a current problem with chlordane, were done a number of studies examining
chlordane metabolites in breast milk. Almost all studies have confirmed the presence
of chlordane in the mother’s milk of women living in areas where chlordane was
used as an insecticide in agriculture and for the home destruction of termites
(Solomon and Weiss 2002). Chlordane can affect the digestive and nervous system.
High exposure can cause convulsions and death. Additionally, exposure to herbi-
cides and insecticides is especially harmful to the thyroid; chlordane is one of the
most toxic chemicals in this regard (Goldner et al. 2011).
DDT was widely used during World War II to protect soldiers and civilians from
malaria, typhus, and other diseases spread by insects. After the war, DDT continued
to be used to control disease, and it was sprayed on a variety of agricultural crops,
especially cotton. DDT continues to be applied against mosquitoes in several
countries to control malaria. The best-known toxic effect of DDT is described as
Silent Spring – book which documented the death of birds resulting from the aerial
spraying of DDT to kill mosquitoes. Researchers discovered that earthworms were
accumulating the persistent pesticide and that the birds eating them were being
poisoned. These evidences led to a nationwide ban on DDT for agricultural uses
and inspired an environmental movement that led to the creation of the US Envi-
ronmental Protection Agency (Paull 2013).
Heptachlor is a nonsystemic stomach and contact insecticide, used primarily

against soil insects and termites. It was used extensively in the 1960s and 1970s in
household and agricultural settings. Studies link heptachlor to cancer, endocrine
disruption, and developmental toxicity. Heptachlor is readily converted to more
potent heptachlor epoxide (HE) once it enters the environment or the body. A
group of scientists (Cassidy et al. 2005) from USA have worked on determination
of the levels of HE, oxychlordane (OC), and dichlorodiphenyldichloroethylene
(DDE) in adipose tissue within breast biopsies in a series of 34 women evaluated
for breast abnormality. They have shown that HE increases oxidant levels that
damage DNA and cell membranes by a 17b–E2 receptor-mediated process and
they proposed that HE-induced DNA damage may contribute to breast cancer in
exposed women.
Heptachlor began to be phased out in the late 1970s but its use was not banned
until. Its only legal use today is to kill fire ants in power transformers and in
underground cable television and telephone cable boxes (ATSDR 2005b).
Industrial Chemicals
Polychlorinated Biphenyls
Polychlorinated biphenyls (PCBs) are persistent organic pollutants (POP) that once
released into the environment remain there a long time (many years) because they
are resistant to photolytic, biological and chemical degradation. PCBs are found in
the ground, groundwater, and surface water, and mostly in the air. Because of their
nonsolubility in water, they accumulate in fatty tissues of living organisms. In large
concentrations are found in the higher levels of the food chain (birds, fish, mammals,
people). As a consequence of their bioaccumulative characteristics, they often occur
in organisms of humans and animals who live far from the source of PCBs.
These organic compounds commonly enter into living organisms through the
food and the consumption of fish, poultry meat, and dairy products. Often comes to
occupational exposure to PCBs, and there are also accidental poisonings by rela-
tively high doses of these compounds. PCBs are extremely dangerous for workers
who work on maintenance and repair of transformers because PCB concentrations
there are much larger compared to other areas (Stojić et al. 2014), such as the air in
buildings that have electrical devices containing PCB or the air in the external
environment, including the air in hazardous and toxic waste landfills. Exposure to
individuals to PCBs can lead to certain harmful effects to the health of humans and
animals. These effects usually include neurological disorders, disorders of liver
function and reproductive system, change in behavior, disorder of the immune and
endocrine systems, and carcinogenic effects. Especially sensitive to the presence of
PCBs are babies and fetals that are in the phase of development since these
compounds can pass through the placenta and are excreted in breast milk (Shea
et al. 2007). Fortunately, application and production of PCBs has been banned for
several decades, and so their levels in the environment are continuously decreasing.
PCBs have been released in the environment only as a result of human activity.
Their atmospheric transport depends on the number of Cl atoms. Biphenyls with 0–1
chlorine atom remain in the atmosphere, those with 1–4 chlorines gradually migrate
toward polar latitudes in a series of volatilization/deposition cycles, those with 4–8
chlorines remain in midlatitudes, and those with 8–9 chlorines remain close to the
source of contamination (Wania and Mackay 1996). PCBs in the air usually come
from evaporation from the ground or water surface. Once they come in the environ-
ment, further they can be transformed and degraded depending on their structure.
The different structure of PCBs and therefore the different degree of toxicity
imposed the development of risk assessment regulations. The toxicity of any PCB
congener is dependent upon both the number and position of each chlorines on the
biphenyl ring. PCB congeners with a higher number of Cl atoms also have higher
toxicity. However, PCBs with chlorines in the ortho positions of each ring (positions
2, 20 , 6, and 60 ) are less toxic than non-ortho or mono-ortho PCBs. Non-ortho PCBs,
also known as the coplanar PCBs, bind the aryl hydrocarbon receptor (AhR) and are
capable of producing dioxin-like effects within biological systems. In accordance
with that, two groups of PCBs are separately observed: dioxin-like and nondioxin-
like PCBs. There are 12 dioxin-like PCBs with similar structure as TCDD (2,3,7,8-
tetrachlorodibenzo-p-dioxin) (Fig. 2).
Indicator of toxicity for these compounds is toxic equivalency factor (TEF). The
reference congener is the most toxic TCDD which per definition has a TEF of
1 (Birnbaum et al. 2006). TEF takes into account chemical structure and behavior of
chemical compound. For each chemical, the model uses comparative measures from
individual toxicity assays, known as relative effect potency (REP), to assign a single
Fig. 2 Structural formula

of TCDD
Table 6 TEF values for Congeners TEF values

PCB congeners
Non-ortho PCB
PCB 77 0.0001
PCB 81 0.0003
PCB 126 0.1
PCB 169 0.03
Mono-ortho PCB
PCB 105 0.00003
PCB 114 0.00003
PCB 118 0.00003
PCB 123 0.00003
PCB 156 0.00003
PCB 157 0.00003
PCB 167 0.00003
PCB 189 0.00003
scaling factor known as the TEF. TEFs are determined using a database of REPs that
meet WHO (World Health Organization) established criteria, using different biological
models or endpoints and are considered estimates with an order of magnitude of
uncertainty (Van den Berg et al. 1998). By applying the appropriate TEF to each dioxin
congener, the expert toxicologist can calculate a toxic equivalent (TEQ) which expresses
the total toxicity of a mixture of dioxins. TEF values for PCB congeners are given in
Table 6 (Van den Berg et al. 2006).
Polybrominated Diphenyl Ethers (PBDE)

Tetrabromodiphenyl ether, pentabromodiphenyl ether, hexabromodiphenyl ether, and
heptabromodiphenyl ether are PBDEs added to the list of Stockholm Convention for
POPs in 2009. PBDE are industrial chemicals that are used more than 40 years mostly
as flame retardants. In the environment are usually released during their production
process and use as well as during the process of servicing appliances containing
PBDE, their improper recycling and disposal in landfills. Another source of PBDEs
can be the old, discarded furniture that falls apart under the influence of atmospheric
conditions (sun, wind, rain, extreme temperatures) in tiny particles that become part of
the soil, air, and groundwater. Human uptake is thought to be through inhalation,
dermal absorption, and consumption of contaminated food. These chemicals are
among the most toxic chemicals ever synthesized. There are evidences that they
cause cancer (Wenning 2002), and also they cause damage to the central and periph-
eral nervous systems (Banasik and Suchecka 2011), diseases of the immune system
(Fernie et al. 2005), reproductive function disorders (Kodavanti et al. 2010), functional
disorders of the endocrine system (Goldner et al. 2011), and most importantly they
affect neurological development and growth (Dingemans et al. 2011).
Unintentionally POPs
They are an unwanted product of combustion or some chemical process.

Unintentionally, POPs are divided into three groups: polycyclic aromatic hydrocar-
bons (PAHs), dioxins, and furans.
Polycyclic Aromatic Hydrocarbons (PAHs)

PAH (Fig. 3) are organic substances which are widespread in the environment. The
EPA (US EPA 2014) listed 16 PAHs on a list of priority pollutants since they are
considered either possible or probable human carcinogens.
Fig. 3 Structural formula of

PAHs (benzo[a]pyrene)
The most frequent sources are the anthropogenic activities such as: production of
coal and coal tar, asphalt, aluminum, petroleum refineries, and motor exhaust. But,
there are also natural sources of PAHs like open burning, volcanic activities, and
natural losses or seepage of petroleum or coal deposits. PAHs from the air are
disintegrated by the action of sunlight and from the water and soil by the action of
microorganisms over a period of 1 week to a month. However, some of them remain
for years in the soil, underground waters, and sediments of rivers, lakes, and seas.
Investigations on experimental animals have shown that PAHs cause mutagenic and
carcinogenic changes and therefore assume that they are potentially mutagenic and
carcinogenic to humans. Based on the available evidence, both the International
Agency for Research on Cancer (IARC 1987) and the US EPA (US EPA 1984)
classified a number of PAHs as carcinogenic to animals and some PAH-rich mixtures
as carcinogenic to humans. PAHs are associated with lung cancer, so smokers who
inhale smoke containing more PAHs are particularly vulnerable. A study conducted
in the United States (McCarty et al. 2009) showed that daily exposure to PAHs at
smokers is 30 times higher than for others.
Dioxins and Furans

Dioxins are the most widespread toxic chemicals in the environment, which are the
result of technological activities of man. Dioxins are not water-soluble but are highly
soluble in fats and tend to accumulate in higher animal species, including humans.
They are volatile and easily transmitted over long distances, and so they are
transnational environmental pollutants belonging to a group of persistent organic
pollutants. The name dioxin refers to a large group of 210 different dioxin com-
pounds and furans, with 17 of them being extremely toxic. The most prominent and
most toxic dioxin compound is 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). They
are unintentional nus-products of various processes (industry – manufacture of other
chemicals, such as pesticides and dyes, steel production, paper bleaching, household
– wood burning, natural disasters, and incidents – forest fires, volcanic eruptions,
and uncontrolled incineration of hazardous waste). Therefore, dioxins and furans are
most commonly found in the air.
One of the most famous poisoning with dioxins is the use of a chemical sub-
stance, the so-called “Agent Orange,” which the US military used as a herbicide for
the destruction of the rainforest in which the enemy was hiding from 1961 to 1971 in
the Vietnam War. This herbicide is a mixture of 2,4-dichlorophenoxyacetic acid
(2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), which contains the most
toxic dioxin TCDD, which is the cause of poisoning in the Vietnamese population
and war veterans of the United States. Dioxins and furans are carcinogenic and can
cause problems in reproduction and development (Yonemoto 2000). They destroy
the immune system (Radenkova-Saeva 2009) and interfere with the hormonal
system. The biggest problem for humans is that they are very slowly decomposed
and accumulated in the body; therefore, this is why chronic exposure to dioxins is
particularly dangerous for human health.
Analytical Methods
The choice of analytical methodology depends largely on the sample matrix (sample
type) and the chemical structure of the target analytes. Collection of a sample and its
preparation for analysis is a very important step in the analytical procedure. Most
POPs in water are sampled by the use of a conventional bottle sampling technique,
whereby a precleaned sampling bottle is immersed into a target water body, usually
with the help of a water pump. Passive dosimetry technique is also used, with which
analytes can be isolated and preconcentrated at the same time. A review of some
parameters characterizing some of the passive dosimeters from water and most
commonly used over the last 15 years sample preparation techniques has been
published by a group of authors (Tankiewicz et al. 2011). According to them, the
most commonly used passive dosimeters are polar organic chemical integrative
sampler, trimethylpentane-containing passive sampler, and membrane-enclosed
sorptive coating. With the use of passive dosimeters, there are fewer steps in the
analytical procedure, which means results are more reliable and reproducible. After
sampling, the sample should be isolated and preconcentrated, which is also an
important step in the analysis due to their low concentration. Liquid–liquid extrac-
tion (LLE) and solid-phase extraction (SPE) are the oldest and at the same time the
most frequently applied sample-handling techniques in the determination of POPs in
water. LLE is perhaps the simplest but not the best technique. LLE uses a large
amount of toxic solvents like dichloromethane, mixtures of petroleum ether and
dichloromethane or hexane and dichloromethane. In order to avoid this disadvan-
tage, some changes were made as it is liquid–liquid microextraction (LLME),
dispersive liquid–liquid microextraction (DLLME) (Berijania et al. 2006), and
ionic liquids DLLME (IL-DLLME) (Lijun et al. 2009; Diao et al. 2016). These
techniques are rapid, simple, and eliminate the need to cleanup of the extract and use
only few microliters of solvents. Despite the advantages of these microextraction
techniques, SPE is still widely accepted as the best technique for isolating POPs in
water samples, because it is fast, precise, cheap, and uses a small amount of solvents
(Pucarevic et al. 2017).
For soil samples, traditional sample preparation methods (liquid-liquid extraction,
Soxhlet extraction, etc.) are still used. But they are laborious, time consuming,
expensive, and require large amounts of organic solvents and usually involve
many steps, leading to loss of some analyte quantity. As a result, modern sample
preparation procedures, such as accelerated solvent extraction (ASE) have been
developed to overcome the drawbacks of the traditional approaches (Đurović and
Đorđević 2011). ASE technique is equivalent to US EPA Methods (US EPA 3540,
3550, 8150) for the extraction of organochlorine pesticides (OCPs), organophos-
phorous pesticides (OPPs), semivolatiles or base neutral acids (BNAs), chlorinated
herbicides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphe-
nyls (PCBs). The accelerated solvent extraction technique complies with US EPA
Method (US EPA 3545A) for these compounds and is an extraction technique that
significantly streamlines sample preparation. This technique uses extraction solvents

at elevated temperatures and pressures to increase the kinetics of the extraction
process. The high pressure allows the solvent to be used above its boiling point,
keeping it in a liquid state, and thus decreases the amount of time and solvent
required to extract the desired analyte from the sample matrix. Accelerated solvent
extraction technique replaces extraction techniques such as Soxhlet, sonication, and
wrist-shaker with equivalent or better results. Other, but not less important, tech-
niques that used are: supercritical fluid extraction (SFE), microwave-assisted extrac-
tion (MAE), solid-phase extraction (SPE), solid-phase microextraction (SPME),
matrix solid-phase dispersion (MSPD) extraction, and QuEChERS (quick, easy,
cheap, effective, rugged, and safe). It should be indicated that SFE, ASE, and
MAE are instrumental techniques and often use SPE and SPME for purification of
obtained extracts, and also its concentration in case of SPME.
The separation and detection of most POPs are usually accomplished by GC
coupled with several types of detectors, such as electron capture detector (ECD) and
MS detector or high pressure liquid chromatography (HPLC) (Pandit et al. 2002).
Identification based only on chromatographic analysis (retention time) without the
use of spectrometric detection is not suitable as confirmatory method, so MS
detection has found to be indispensable for high sensitivity and unambiguous
detection, confirmation, and determination of such residues in different matrices
(EU Commission Decision 2002/657, 2002).
In summary, with the improvement of the sensitivity of analytical instruments, the
POPs list is increasing, sample volume/mass used for extraction/ analysis and the
volume of solvents used is decreasing. All of this contributes to the protection of the
environment and to a better quality of life.
Remediation
In many courtiers around the world, including the most developed countries, there
are a large number of contaminated sites on which confirmed the presence of
hazardous and harmful substances in concentrations that pose a significant risk to
human health and the environment. While it is difficult to quantify, it has been
estimated that the number of contaminated sites, for example, in Australia is
approximately 100.000 with an estimated remediation cost of $5–8 billion. These
values are small compared to the number of contaminated sites and estimated
remediation costs in Europe and USA (Naidu et al. 2010). Soil contamination
requiring cleanup is present at approximately 250,000 sites in the EEA member
countries, according to the recent estimates. And this number is expected to grow.
Potentially polluting activities are estimated to have occurred at nearly three million
sites and investigation is needed to establish whether remediation is required. If
current investigation trends continue, the number of sites needing remediation will
increase by 50% by 2025 (EEA 2007).
Soil contamination is the result of mixing solid and liquid hazardous substances
with the substances that are naturally present in soil. Landfills are the simplest and
most commonly used method of disposing municipal solid waste (MSW). Landfills
pose a potential threat, because they can endanger the quality of surrounding land,
surface, and groundwater. Landfill leachate is one of the main sources of ground-
water and surface water pollution if it is not properly collected, treated, and safely
disposed (Abd El-Salam and Abu-Zuid 2015). Leachate usually contains pollutants
and often toxic substances from waste.
Many locations contaminated with certain pollutants require remediation. There
are different definitions of remediation which differ from country to country but in
general include the implementation of appropriate measures to prevent further
pollution of all environmental factors and restoring contaminated sites in a condition
suitable for use, with no negative impact on the environment and human health.
According to the US EPA (United States Environmental Protection Agency), the
procedure of application specific remediation technology certainly must precede the
identification of present pollutants and assessment of their impact on human health
and the environment (US EPA 2008). After performing the process of identification
and assessment of the effects of pollutants, it is followed by a method of treatment or
removal of the contaminated medium. For the implementation of all these pro-
cedures, the US EPA uses a wide range of technologies, in order to present pollutants
or completely removed from the site or be treated to the point where no longer pose a
threat to human health and the environment (US EPA 2000). In this context,
remediation technologies are referred to as technologies for the treatment or com-
plete removal of pollutants from contaminated media. In Part 2A of the Environ-
mental Protection Act, which came into force in 2000 in England (EA 2009),
remediation is defined as a process involving the breakdown of links between
pollutants and receptors, as well as disabling the routes of transporting contaminants
to the receptor. Often, this involves the removal of pollutants from the location but
also preventing the spread of polluting substances to the receptor, as well as changes
are made in the receptor (e.g., to change the purpose of land, to limit access to
challenge, etc.). In the last two cases, it is not necessary to change the level of
contamination in the soil (Defra 2008).
Changes in legislation on waste in the European Union at the beginning of the
twenty-first century have a significant impact on the classification and methods of
waste treatment but also on the remediation of contaminated soil. The most signif-
icant changes are related to the revision of the European Waste Catalog and the
introduction of the Landfill Directive (Bone et al. 2004). The European Waste
Catalog from 2002 identifies construction waste and demolition waste, including
excavated soil from contaminated sites, as a special waste class (Commission
Regulation (EC) No 574/ 2004).
The Landfill Directive primarily plays an important role in preventing the forma-
tion of contaminated sites from waste disposal, because it (Council Directive 1999):
– Prohibits the disposal of certain waste types (liquid, combustible, explosive,

infectious hospital or slaughter waste, old tires, and other types of waste that do
not meet the criteria set out in Annex II)
– Reducing biodegradable waste disposal
– Prohibits the deposit of untreated waste and the joint disposal of inert, hazardous,
and municipal waste
– Introduces the classification of landfills according to the type of waste that is
deposited on it, etc.
In the Netherlands, for example, the management of contaminated sites policy is

based on two key laws, the Soil Protection Act (Wesselink et al. 2006) and the
Environmental Protection Act (Soil Remediation Circular 2009). Among other things,
the Soil Protection Act is prescribed to take a soil remediation in such a manner that,
after its implementation, soil can be used for the above specified purpose, whereby the
risk for people, animals, and plants from exposure to contamination must be mini-
mized. The law also stipulates that remediation must be performed in such a way that
as much as possible reduce the possibility of the spread of contamination in the
surrounding area as well as to reduce the necessity of taking accompanying measures
and the limited use of land after treatment (Soil Remediation Circular 2009).
There are a number of technologies for the treatment of contaminated soil. In
selecting appropriate technology for the treatment or elimination of pollutants from
the soil should be taken into account a number of factors. The most important are the
type of pollutants at the site, the level or degree of contamination, the possible
consequences for the living world, the surface of the contaminated medium, the
location, etc. One of the most important factors is also the level of financial
investment required for the implementation of certain technologies, which also
should not be decisive for the choice of appropriate technology, especially because
any delay and inadequate choice can have significant and lasting effects (Jaksic and
Ilic 2000).
Soil Pollution Caused by the Disposal of Solid Waste to Unsanitary

Landfills
Soil pollution is defined as the presence of contaminants in soil, in high enough

concentrations to pose a risk to human health and/or the ecosystem. In the case of
contaminants which occur naturally in soil, even when their levels are not high enough
to pose a risk, soil pollution is still said to occur if the levels of the contaminants in soil
exceed the levels that should naturally be present (Regulation 2010). According to EU
regulations (Commission of the European Communities 2006), soil contamination is
discussed when in the soil identifies the presence of pollutants above the prescribed
level, causing deterioration or loss of one or more soil functions. The most common
causes of soil contamination are associated with human activities, which result in the
emission of artificial chemicals into naturally occurring soil components, which
disturbs the natural balance and causes adverse effects on human health and the
environment. This type of contamination most often derived from the leaching of
hazardous and harmful substances from the above-ground tanks, the use of pesticides,
the penetration of contaminated surface water in the lower layers of the soil and
groundwater, leaching of pollutants from the unsanitary landfills, etc. The most
common causes of soil contamination are petroleum hydrocarbons, solvents, heavy

metals, etc. The occurrence of these phenomena is correlated with the degree of
industrialization and the intensity of use of chemicals.
The link between soil contamination and waste management is more than obvi-
ous. Inadequate waste management leads to the formation of a large number of
contaminated sites. Advanced waste management systems which include the
recycling of waste in construction products or fertilizers can also be positively or
negatively affect the quality of the soil. Modern landfills, having elements of the
sanitary protection, are designed to prevent contamination of the surrounding soil,
surface water, and groundwater (Van Camp et al. 2004). In case of unsanitary
disposal of municipal and other waste streams, there is an uncontrolled distribution
of pollutants from the disposed waste, which indicates the possibility of contamina-
tion of the soil and other environmental media. Lack of the protective synthetic liner
and system for collection of leachate at landfills for inert, nonhazardous or hazardous
waste is a problem due to the migration of pollutants into surrounding soil, under-
ground, and surface waters (Ismail et al. 2003).
Sources of Soil Pollution

In the literature, there are many different classifications of soil pollution sources.
Caliman et al. (2011) claim that the following activities mostly lead to pollution of
soil and groundwater:
– Leaching from unsanitary landfills.

– Uncontrolled dumps.
– Accidental discharge of chemical and waste materials.
– Inadequate storage of liquid waste.
– Setting up a system for collection of sewage wastewater in hydrologically and
geologically inappropriate locations.
– Inadequate application of fertilizers and pesticides in agriculture, etc.
In terms of soil contamination, the major problem is technology that gives a large
amount of waste. It is estimated that around 25 billion tonnes of raw materials are
processed annually in the world, from 1 to 1.5 billion tonnes in finished products, while
the rest is waste that requires adequate treatment and disposal (Kastori et al. 2006).
The European Environment Agency (EEA) has estimated that about three million
sites in the EU countries potentially threatened by anthropogenic activities that take
place on them, of which 250,000 locations requires cleaning (EEA 2007). Considering
the current trends, the EEA estimated that the number of contaminated sites would
increase by 50% by 2025 (Caliman et al. 2011). On the basis of the conducted
investigations on contaminated sites in Europe, the most important sources of contam-
ination are industrial activities, the treatment and disposal of waste (Fig. 4).
Pollutants in Soil
In order to successfully protect soil from pollution, it is necessary to know the
sources of pollution but also the quantity and characteristics of pollutants and their
Others
Military
8.2%
Mining 0.9%
1.4%
Transport spills on land
2.1%
Power plants
3.9%
Industrial production and
Storage commercial service
5.4% 41.4%
Industrial waste treatment

and disposal
7.3%
Oil industry
7.3%
Municipal waste treatment

and disposal
15.2%
Fig. 4 Overview of activities causing soil contamination in Europe (EEA 2007)
harmful effects. The number and type of pollutants are unlimited, as they constantly
change and complement depending on the applied technologies, the degree of
urbanization, etc. (Kastori et al. 2006).
Generally, the pollutants or contaminants are substances that can damage or
pollution of the environment, regardless of whether they are naturally present in
the environment or have been released from an industrial process or other human
activities. Kostic (2007) under the pollutant means any physical, chemical, biolog-
ical or radioactive, gaseous, liquid or solid matter or substance that reduces the
natural quality of water, soil, or air.
Although there are many classifications of pollutants, which are used in the
examination of the contaminated areas, in the broadest sense they can be divided
into organic and inorganic.
Gradel (1978) argues that organic substances constitute a large group of over 1600
chemicals of natural and anthropogenic origin that are present in a natural and polluted
environment. Among the most important polluting substances of organic origin are:
products from the oil refining process, such as petroleum hydrocarbons, organochlo-
rine compounds, such as pesticides or polychlorinated biphenyls, dioxins, and furans,
etc. In the waste, organic pollutants may occur in the form of soluble compounds or as
complex mixtures with other compounds, including inorganic pollutants.
Many organic pollutants possess hazardous characteristics. US EPA (1992)
defined hazardous substances as having at least one of the following characteristics
of hazardous substances: toxicity, corrosivity, self-inflammability, and chemical
reactivity. Kastori et al. (2006) define hazardous substances as toxic substances

(carcinogenic, teratogenic, and mutagenic), persistent or susceptible to
bioaccumulation. One of the most important groups of hazardous pollutants are
persistent organic compounds (POPs) that are not changing in the environment or
their disappearance is so slow that they are accumulating in parts of the ecosystem.
Most of the polluting substances of organic origin are toxic at very low
concentrations.
Typical inorganic pollutants in soil are heavy metals and metalloids. In addition to
theme, other cations and anions that pose a significant risk to the receptors in the
environment can be found in the soil.
Heavy metals in the environment may be naturally present or may be of anthro-
pogenic origin. Unlike metals that come into the environment by human action,
natural metals in the environment are present at relatively low concentrations. In
recent years, the number of metal anthropogenic sources increases which causes a
significant increase in their concentration in the environment. The most important
sources of metal emissions into the environment are dumps, transportation means,
mines and molten metals, organic mineral fertilizers, sludge from a wastewater
treatment plant, etc. (Granero and Domingo 2002).
Heavy metals represent pollutants that are unchangeable, nonbiodegradable, and
persistent in the soil. Although the soil has a natural capacity to mitigate bioavailability
and the movement of metals by means of different mechanisms (precipitation, adsorp-
tion, and redox reactions), when heavy metal concentrations become so large that they
overcome the natural regulatory capacity of the soil, their mobilization results in
contamination of agricultural products and groundwater. In these cases, it is necessary
to take all necessary measures for the remediation of contaminated soil (Shi et al. 2009).
Knowing the physical and chemical characteristics of pollutants present in the
soil allows predicting their mobility and the success of the remediation process.
According to the literature data (Bone et al. 2004), chemical interactions of
pollutants with soil primarily depend on the phase in which the pollutant is located
(solid, liquid or gas), its solubility, soil mineralogy, pH values, and the amount of
organic matter present in the soil. Williams et al. (2002) point out that naturally
occurring organic matter in the soil most often react and form complex compounds
with metals. Depending on the solubility of newly formed complex compounds,
there is a decrease or increase in the mobility of metals in the soil. Thus, monitoring
of the reactions between soil and pollutants and the parameters of the environment in
which they occur is very important for determining the fate of pollutants and the
risks that their presence in the soil represents for human health and the environment.
The main phenomena that describe the reaction between the pollutants, soil, and
water in the pores of the soil are:
– Sorption (physical or chemical adsorption).

– Oxidation-reduction reactions.
– precipitation.
– Hydrolysis.
– Biological degradation.
The Criteria for the Classification of Contaminated Soil
Soil classification depending on the presence of pollutants is very important because

it determines the extent to which the soil is contaminated, whether it poses a risk to
human health and the environment, or whether its remediation is required.
In many countries around the world, different soil classification is applied,
depending on the degree of presence of pollutants. In USA, each state shall prescribe
permissible content of pollutants in the soil and accordingly determines the classi-
fication of contaminated soils. In USA, soil is generally categorized as follows
(Kurisko et al. 1998):
– Soils containing hazardous wastes – require “on-site” remediation or “off-site”

management of soil as hazardous waste.
– Nonhazardous soils.
– Soils containing pollutants below the values that require cleaning.
In the European Union, the soil protection framework is the COM (2006) 232 final
amending Directive 2004/35/EC (Environmental Liability Directive, ELD) which
establishes a framework to prevent and remedy environmental damage. Although all
member states are obliged to apply the provisions of Directive COM (2006) 232 final,
it did not define the limit values for remediation of hazardous and harmful substances
in soil and each member state defines the aforementioned criteria.
In the Netherlands, there are precisely defined maximum permissible concentra-
tions for the content of pollutants (metals, other inorganic substances, aromatic
compounds, polycyclic aromatic hydrocarbons, chlorinated hydrocarbons, etc.) in
soil and groundwater. In this sense, the contaminated soil is classified as soil where it
is not required or requires remediation. Soil remediation projects are performed if the
average concentration of any hazardous or harmful substances of more than 25 m3
volume area exceeds the prescribed value (Soil Remediation Circular 2009).
In many countries of the world, there are clearly defined criteria for classifying
contaminated soil as waste. European Waste Catalogue, adopted in 1994, introduced
a new method of classification and treatment of waste, including the remediation of
contaminated soil. The legal basis for the European Waste Catalog makes Directive
75/442/EEC on waste, as amended by Directive 26/12/EC. According to the require-
ments of Directive 91/689/ EC on hazardous waste, the Council of Europe has made
Decision 94/904/EC defining a list of wastes from the Waste Catalogue that have
hazardous characteristics, known as the list of hazardous wastes (Council Decision
1994). Contaminated soil is not identified on the hazardous waste list but is catego-
rized as special waste, unless it has one of the hazardous characteristics of the H list
(from H3 to H8), which presents a list of characteristics of waste that make it
hazardous. The European Waste Catalog has been periodically revised and updated.
In the latest version of the European Waste Catalog, there are several waste groups
and a separate group of wastes consists of group 17 which includes construction and
demolition waste (including excavated soil from contaminated sites). The Catalog
within the group 17 as a subgroup of 05 states soil (including soil excavated from
contaminated sites) and rock excavation. Within this subgroup, the index numbers of
03–08 different categories of soil referred to as waste, including hazardous waste.
The Criteria for the Remediation and the Remediation

of Contaminated Sites
Under the remediation of polluted sites, in the broadest sense, it means the imple-
mentation of all measures and activities for eliminating the danger to humans and the
environment caused by the release of pollutants.
With the aim of reducing and preventing soil contamination in numerous studies
and research, various technologies for the remediation of soil contaminated with
pollutants of organic and inorganic origin have been developed and applied. The
choice of suitable technology is complex but a very important step in the successful
implementation of the remediation (Khan et al. 2004). After conducting an analysis
of the presence and concentration of pollutants in the soil, as well as assessments of
their impact on human health and the environment, making a decision on the choice
of remediation method is a key step in remediation of contaminated soil. When
choosing technology, it is also important to conduct an analysis of the effectiveness
of alternative remediation methods in removing contaminated pollutants from the
contaminated medium, as well as economic analysis, or determining the amount of
financial investments needed to perform remediation.
The Process of Risk Management in the Context of the Remediation

of Contaminated Sites
For the adoption of appropriate decisions on the treatment of contaminated sites is

crucial to assess the degree of risk that contamination has on human health and the
environment.
The risk is most often estimated on the basis of the total concentration of pollutants
in the soil and on the basis of other factors such as: land use (agricultural, land in
residential or recreational zones, industrial, etc.), including limit values of pollutant
content for certain uses soil and level of contamination (Sahuquillo et al. 2003).
Risk management, which may occur as a result of soil contamination or the
management of waste streams, includes procedures that include identification, assess-
ment, and final risk assessment, taking into account procedures for their prevention or
mitigation, monitoring, and follow-up monitoring. Therefore, the risk management
process in the context of the remediation of contaminated sites is a wider concept of
the risk assessment and coverage process (Marjanović et al. 2009):
– Risk assessment: determining whether there is an unacceptable risk and, in case

there is, identification of further activities to be undertaken at the site.
– Evaluation of options: evaluation of feasible options for remediation and deter-
mining the most appropriate strategy for the remediation site.
– Implementation: implementation of remediation strategy and demonstration of its

efficiency in the present and in the future.
Risk assessment is used as a formal instrument of environmental policy by which

it determines the way of dealing with contaminated media. US National Research
Council (NRC) recognizes four levels of risk assessment (Ferguson et al. 1998):
– Hazard identification: identifying agents that can cause side effects.

– Dose–response ratio: estimation of the quantitative relationship between expo-
sure and adverse effects confirmed by laboratory experiments or epidemiological
tests.
– Exposure analysis: estimation of intensity, frequency of occurrence and duration
of exposure to hazardous agents (most often involves transport and fate of
pollutants in underground and surface waters).
– Risk characterization: evaluation and conclusions based on the results of previ-
ously conducted steps.
Methods and Techniques of Performing Remediation
Remediation can be conducted in a way that implies (Kostic 2007):
– Complete removal of pollutants – restoring the polluted area to the state before
pollution, what is possible, but technically difficult to implement and financially
very demanding solution.
– Reduction of pollutants in the contaminated soil to an acceptable level.
– Immobilization and blocking pollutants in contaminated media, which does not
involve the removal of pollutants, but their immobilization or preventing their
movement.
For each of the above-mentioned modes, there are different technical possibilities.
For example, it is possible to remove or treat pollutants using various physical,
chemical, and biological agents.
All technologies for remediation of various environmental media can be classified
into two main groups, namely (Jaksic and Ilic 2000):
– In situ technologies – technologies used on-site mainly for the treatment of large
areas of contaminated soil, sediment, large amounts of water, and for milder
forms of contamination.
– Ex situ technologies – technologies in which the removal of contaminated
media (soil, sediment, water) is first performed and its further processing is
carried out at another location. This kind of processing is most often used when
it comes to extremely contaminated media, small surfaces and quantities, as
well as treatments that require special conditions (high temperature, extraction,
etc.).
Table 7 Technologies In situ technologies Ex situ technologies

for soil remediation to
Biological processes
the place of application
(Kostic 2007) - Bioventilation - Biodegradation in liquid
- Biostimulation state
- Phytoremediation - Biodegradation in soil state
-Natural remediation
Abiotic processes
Physical-chemical processes
- Steam extraction (vacuum - Stabilization /
extraction) solidification
- Stabilization / solidification - Vitrification
- Vitrification - Washing
- Chemical reduction-oxidation - Chemical reduction-
- Washing oxidation
(a) Other processes - Chemical extraction
- Surface cover (b) Thermal processesa
(c) Other processes
- Excavation of
contaminated land
Thermal processes
- desorption
- burning
- pyrolysis
- open burning
a
In the in situ process, heat is supplied as part of another process
Technology for the remediation of soil using biotic or abiotic (physical, chemical,
or thermal) processes. They may be applied at the site where pollution is found
(in situ remediation) or outside the site of pollution (ex situ remediation), when the
land pre-excavated and treated in a different location. The following table presents
the division of soil remediation technologies to the site of application (Table 7).
Conclusion
In the modern world, the major problem is the large area of contaminated sites
requiring remediation and restores a state suitable for use. A large share of contam-
inated sites is derived from waste materials that are inadequate and often improperly
disposed directly on the soil. As a result of the mixing of solid and liquid waste
materials with substances that are naturally present in the soil, sites whose future use
are disabled and which, without recovery, represent a lost natural resource.
There are a number of technologies for the treatment of contaminated soil. In
selecting appropriate technology for the treatment or elimination of pollutants from
soil should be taken into account a number of factors. The most important are the
type of pollutants at the site, the level or degree of contamination, the possible
consequences for the living world, the surface of the contaminated medium, the
location, etc.
During remediation, it is possible to simultaneously apply several different

methods. An individual remediation method may support numerous activities or
operations for the reduction or complete elimination of pollutants. However, in some
cases it is not enough to apply one method to solve all the problems that exist at the
site. It is possible that one method is suitable for the treatment of certain pollutants,
while it is not suitable for the treatment of others. In order to ensure the efficiency of
such surge remediation strategies and ensure its practical applicability, it is necessary
to carefully and detailed planning and design.
The aim of this chapter is to contribute to faster and more efficient decision-
making and to expand current knowledge about how to perform effective remedia-
tion. It should also help the participants in the process of remediation to understand
and apply the necessary remediation measures and use the end product of remedi-
ation in the form of useful products. It is extremely important to help and understand
the concept of sustainable waste management as a measure of prevention for the
recovery and remediation process.
Cross-References
▶ Monitoring and Risk Analysis of PAHs in the Environment
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Part III
Hazardous Waste Management
Development of an Environmentally
Sustainable Approach for Safe Disposal of 24
Arsenic-Rich Sludge
Pankaj Kumar Roy, Arunabha Majumder, Somnath Pal,

Gourab Banerjee, Malabika Biswas Roy, Jayanta Debbarma, and
Asis Mazumdar
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 620
Treatment Methods for Arsenic-Rich Sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624
Preparation of Arsenic-Rich Sludge by Employing Oxidation and Precipitation
Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624
Arsenic Concentration in Filtered Supernatant Water After Coprecipitation . . . . . . . . . . . . . . . 625
Preparation of Concrete (M15-1:2:4) with Arsenic-Rich Sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
Use of Arsenic-Rich Sludge in Brick Manufacturing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 627
Disposal of Arsenic-Rich Sludge in Anaerobic Bioreactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 627
Arsenic-Rich Sludge Used for Concrete Cubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 628
Arsenic-Rich Sludge Used in Brick Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 628
Arsenic-Rich Sludge Stabilization in Anaerobic Bioreactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 630
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 632
Abstract
Arsenic contamination in groundwater has been reported by many researchers
from different parts of the world. In West Bengal, arsenic contamination in
P. K. Roy (*) · S. Pal · G. Banerjee · A. Mazumdar

e-mail: pk1roy@yahoo.co.in
A. Majumder
M. B. Roy
Women’s College, Calcutta, Kolkata, India
J. Debbarma
PWD (Water Resources), Agartala, Tripura, India

https://doi.org/10.1007/978-3-319-73645-7_14
620 P. K. Roy et al.
groundwater was first detected in 1983 when a few patients with arsenicosis
reported at the School of Tropical Medicine, Kolkata. Today, arsenic
contamination in groundwater is found to be affecting 82 blocks of eight districts
of West Bengal, namely, Maldah, Murshidabad, Nadia, North 24 Parganas, South
24 Parganas, Burdwan, Hooghly, and Howrah, and also in 11 municipal areas and
18 non-municipal outgrowth areas.
Providing safe drinking water to people in rural community is a major chal-
lenge in arsenic-affected areas in and around the world. One of the options for
supplying arsenic-free and potable water is to remove arsenic from contaminated
groundwater, and the second option is to provide potable water filtered from
surface water system by various mechanical filtration technologies. Both these
options involve a huge amount of cost and manpower and adaptation of suitable
engineering methods and economically feasible solutions. On the other hand,
arsenic removal processes generate arsenic-rich sludge which requires safe dis-
posal as because the sludge becomes hazardous.
Disposal of arsenic-rich sludge generated from contaminated water by the
method of coprecipitation and adsorption is a major environmental concern.
Qualitatively arsenic-rich sludge is hazardous, and uncontrolled disposal may
lead to environmental degradation. In order to stabilize arsenic-rich sludge, it was
mixed in different proportions with cement concrete and clay soil. In the first
phase of the experiment, the compressive strength of the concrete cubes and
bricks was analyzed, and toxicity characteristic leaching test was conducted to
determine the quantity of arsenic in the leachate. In the second phase, injection of
the sludge into bench-scale anaerobic bioreactors was carried out to monitor the
stabilization of arsenic-rich sludge. The toxicity characteristic leaching test for all
the concrete cubes and bricks indicated the presence of arsenic concentration in
leachate within the permissible limit. The study showed that arsenic-rich sludge
could be potentially disposed through environmentally friendly manner by
mixing with cement concrete and bricks.
Keywords
Adsorption · Compressive strength test · Concrete · Coprecipitation · Leachate ·
TCLP · Groundwater
Introduction
In nature, arsenic (As), in its various forms, is widely presenting both surface and
subsurface of the earth’s crust. It gets introduced in water through dissolution of
minerals and ores and through erosion from natural sources. Arsenic is of major
environmental concern because of its toxicity to plants, animals, and human beings,
although the necessary intake may be as low as 0.01 mg/day (http://www.lenntech.
com/periodic/elements/as.htm). Its presence in natural water may originate from
geogenic formations, geochemical reactions, industrial waste discharge, burning of
arsenic-containing fossil fuels, volcanic eruptions, and arsenic pesticides apart from
24 Development of an Environmentally Sustainable Approach for Safe. . . 621
its existence in soil. Soil is an important natural resource for mankind, but it also
serves as a medium for accumulation, transformation with subsequent disintegration,
and migration of toxicants. The occurrence of arsenic in groundwater is mostly due
to the leaching of geological material (Purkait and Roy 2006), mineral precipitation,
dissolution of unstable arsenic minerals, adsorption-desorption, chemical transfor-
mations within formation, input from geothermal sources, etc. (Purkait and Roy
2006). The arsenic-contaminated groundwater poses serious risk to the people who
depend on groundwater. Consumption of arsenic-contaminated water for a pro-
longed period may cause arsenicosis with serious health disorders.
Arsenic contamination in groundwater has been reported by many researchers
from different parts of the world. In West Bengal, arsenic contamination in ground-
water was first detected in 1983 when a few patients with arsenicosis reported at the
School of Tropical Medicine, Kolkata (Nath and Mazumdar 1999). Today, arsenic
contamination in groundwater is found to be affecting 79 blocks of eight districts of
West Bengal, namely, Maldah, Murshidabad, Nadia, North 24 Parganas, South
24 Parganas, Burdwan, Hooghly, and Howrah, and also in 11 municipal areas and
18 non-municipal outgrowth areas (AIIH & PH 2007). About 42.7 million people
have arsenic levels in groundwater above the World Health Organization (WHO)
maximum permissible limit of 50 μg/L (Chowdhury et al. 2000). Arsenic is basically
found in the eastern part of the river Ganga due to deposition of Late Quaternary
sediments. In order to investigate the mechanism of As released to anoxic ground-
water in alluvial aquifers, the authors sampled groundwaters from 3 piezometric
wells, 79 shallow (<45 m) wells, and 6 deep (>80 m) wells, in an area of 750 m by
450 m, just north of Barasat, near Kolkata (Calcutta), in southern West Bengal
(McArthur et al. 2004). However surface water sources and dug wells were found
free from arsenic contamination.
The provision of availability of safe drinking water is one of the prior conditions
necessary for the overall socioeconomic development. Arsenic in drinking water is a
global problem where as many as 170 million people in over 70 countries have been
affected (IWA 2007). The sinking of tube wells for drinking water in Bangladesh has
in the past been promoted as a means of avoiding waterborne diseases associated
with the consumption of untreated surface water. Unfortunately, the recent discovery
of arsenic in groundwater in Bangladesh has reached up to 2 mg/L, which has led to
describe the situation as a major public health emergency (Allan et al. 2000).The
recent innovation of Sono 3-Kalshi filter (Hussam et al. 2008) could be a landmark
for mitigation of arsenic in the drinking water. Solid waste management in devel-
oping countries is often unsustainable, recycling on uncontrolled disposal in waste
dumps. A particular problem arises from the disposal of treatment residues generated
during removal of arsenic (As) from drinking water because As can be highly mobile
and has the potential to leach back to ground surface waters (Sullivan et al. 2010).
Providing safe drinking water to people in rural community is a major challenge
in arsenic-affected areas in and around the world. One of the options for supplying
arsenic-free and potable water is to remove arsenic from contaminated groundwater,
and the second option is to provide potable water filtered from surface water system
by various mechanical filtration technologies. Both these options involve a huge
amount of cost, manpower, and adaptation of suitable engineering methods and

economically feasible solutions. On the other hand, arsenic removal processes
generate arsenic-rich sludge which requires safe disposal as the sludge is most
hazardous for environment. Appropriate sustainable methods are needed to be
developed for safe disposal of arsenic-rich sludge and engineered media and the
same need to be practiced when arsenic removal units are installed. Whatever may be
the sizes of arsenic removal units, arsenic-rich sludge is considered to be hazardous
waste, and uncontrolled disposal may cause adverse impact on the environment. It is
therefore necessary to provide eco-friendly treatment to arsenic-rich sludge so that
their disposal will not cause any adverse impact to the environment. In the present
study, an appropriate eco-friendly method is designed for safe disposal of arsenic-
rich sludge in order to (a) examine the extent of arsenic richness of sludge, (b) assess
the quantum of sludge generated after treatment, (c) study different methods for
stabilizing sludge and the leach ability of stabilized arsenic-rich sludge through
TCLP testing, and (d), finally, recommend appropriate treatment and safe disposal
system for arsenic-rich sludge.
An environmentally sustainable development framework is needed and is con-
ceptualized through experimental design in the present study considering three
subsystems of economy, society/community, and environmental interaction.
Mostly researchers have been focused on awareness building and the develop-
ment of water treatment system removing arsenic from drinking water. The disposal
of arsenic-rich sludge generated from the different techno-treatment processes is
one of the issues that have received little attention from the sponsors of the
technologies and the users (Eriksen-Hamel and Zinia 2001; Kameswari et al.
2001; Dutre and Vandeeasteele 1995; Akhtar et al. 2000). The solidification or
stabilization process would be the best practical technology to treat the arsenic
waste (Artiola et al. 1990; Voigt et al. 1996; Vandeeasteele et al. 2002; Leist et al.
2003). It is found appropriate by many investigators in treating arsenic-contaminated
wastewater (Fuessle and Taylor 2000; Sanchez et al. 2003; Shih and Lin 2003; Pal
2001). It is further found in one study that the recommended proportion of contam-
inated sludge in brick making is up to 15–25% by weight (Rouf and Hossain 2003).
A similar study was carried out by Banerjee and Chakraborty (2005) where they
used arsenic-contaminated sludge for the preparation of concrete cubes, briquette
production, and cement mortar preparation. The study depicted that arsenic sludge
can safely be utilized for briquette production along with clay up to a proportion of
10% (v/v) with respect to the total mixed ingredients; the leachate formed by TCLP
contains As concentration below its safe discharge limit of 0.2 g/m3 set by the
Central Pollution Control Board (CPCB) under the Ministry of Environment and
Forest (MoEF), Government of India (GOI). Arsenic sludge can be stabilized by
standard cement concrete ingredients up to a proportion of 40% (v/v) with respect to
the total volume of the mixture, and the leachate formed in the TCLP test contains
arsenic below the desired safe discharge limit. However concrete or clay mortar that
is richer in arsenic-laden sludge showed an increase in the amount of leachate
generated. In the preparation of cement mortar, the arsenic-laden sludge could be
blended up to a proportion of around 10% (v/v) with respect to cement content.

Banerjee and Chakraborty (2005) had also shown that replacement of cement by fly
ash up to a proportion of 50% (v/v) of cement results in 45–50% reduction in the
compressive strength of cement mortar at an arsenic sludge content of 10%. Studies
also showed that arsenic-contaminated sludge could be used safely up to 4% for
making ornamental bricks (Mahzuz et al. 2009).
While considering option for waste disposal, it is essential that appropriate
leaching tests are applied and results are correctly interpreted. Leist et al. (2003)
undertook an evaluation of leaching test and commented that they did not model
the conditions that the waste would experience when placed in landfill.
Badruzzaman (2003) reported that the application of TCLP may not be suitable
for assessment of long-term leaching of As from As-rich waste, as such leaching
may be kinetically restricted. Eriksen-Hamel and Zinia (2001) carried out a study
on the leaching characteristics of arsenic-contaminated sludge in some selected
part in Bangladesh like Pabna, Rajshahi, Kachua, Nawabganj, Maijdi, etc. Their
results show that the arsenic concentration in TCLP extraction fluid of different
samples taken from different places toxicity is well below the level of “hazardous
waste.”
Visoottiviseth and Ahmed (2008) carried out different technology option for
remediation and disposal of arsenic. In their study, percentage removal of arsenic
using different technologies, namely, conventional filtration, phytoremediation using
arsenic hyperaccumulating fern, bioremediation using Chlorella vulgaris algae,
combined sand and nano-filtration, reverse osmosis, low pressure nano-filtration
and reverse osmosis, ion exchange, cartridge filter, indigenous filter, adsorption by
activated carbon, activated alumina, lime treatment using calcium oxide or calcium
hydroxide, coagulation and filtration, solar oxidation, chemical oxidation, in situ
oxidation, passive sedimentation, oxidation, etc., has been analyzed, and an alternate
water supply option (arsenic-free) is emphasized. The alternative sources that they
pointed out were deep tube-well dug/ring well, rain water harvesting (RWH), etc.
As far as our study is concerned, different methods have been applied for
assimilation of arsenic sludge such as using arsenic sludge in making concrete
cubes, in preparation of bricks with certain proportion replacement, and using the
same in an anaerobic bioreactor where arsenic is consumed by the anaerobic bacteria
resulting in a decrease in overall concentration of arsenic sludge. The overall
objective of this present research is to explain the management procedure of the
arsenic rich sludge which generated from after treatment of hand pump attached
arsenic removal units (ARUs). Since the units are installed in the rural areas where
fly ash is not abundantly available due to the absence of any thermal power plant in
and around the investigation area, so the research work has done with OPC cement
concrete mixture.
Despite the successful development in the laboratory of technologies for arsenic
remediation, few have been successful in the field. A sustainable arsenic remediation
technology should be robust, composed of local resources, and user-friendly as well
as must attach special consideration to the social, economic, cultural, traditional, and
environmental aspects of the target community. One such technology is in operation

on the Indian subcontinent. Wide-scale replication of this technology with adequate
improvisation can solve the arsenic crisis prevalent in the developing world.
Treatment Methods for Arsenic-Rich Sludge
The arsenic-rich sludge is prepared by employing oxidation and precipitation

processes and in filtered supernatant water after coprecipitation. The following
preparation methods are employed to prepare the arsenic-rich sludge:
(i) Preparation of concrete (M15-1:2:4) with arsenic-rich sludge

(ii) Use of arsenic-rich sludge in brick manufacturing
(iii) Disposal of arsenic-rich sludge in anaerobic bioreactor
(iv) Arsenic-rich sludge used for concrete cubes
(v) Arsenic-rich sludge used in brick preparation
(vi) Arsenic-rich sludge stabilization in anaerobic bioreactor
Preparation of Arsenic-Rich Sludge by Employing Oxidation

and Precipitation Processes
Arsenic stock solution (1000 mg/L) was added in requisite proportion to prepare
spike solution of arsenic having an arsenic concentration of 0.5 mg/L. Arsenic-rich
sludge in bulk quantum was generated at the laboratory of the School of Water
Resources Engineering, Jadavpur University. Bleaching powder and alum were
added in arsenic-contaminated water at the rate of 5 mg/L and 70 mg/L, respectively.
Both the chemicals were rapidly mixed for 60 s to generate the effect of coagulation.
It was then followed by slow mixing for 10 min for development of aluminum
hydroxide flocs. The water in the container was then allowed to settle for 2.5 h. The
concentrated arsenic-rich sludge was collected as bottom sludge after draining out
the supernatant.
The quantum of sludge could be estimated as follows:
Al2 ðSO4 Þ3 2AlðOHÞ3

:18 H2 O þ 3 CaðHCO3 Þ2 ! þ 3 CaSO4 þ 3 CO2 þ 18 H2 O
ð666Þ ð156Þ
In a 15 L bucket filled with arsenic-contaminated water (As-0.5 mg/L), 1.05 g of

alum was added. In the process aluminum hydroxide of 0.246 g was formed. The
supernatant water after coprecipitation process was found to contain 0.03 mg/L of
arsenic. The arsenic content in raw was analyzed as 0.53 mg/L as depicted in Table 1.
So arsenic adsorbed by aluminum hydroxide was estimated to be around 7.05 mg.
The total dry weight of arsenic-rich sludge formed by coprecipitation process in a
Table 1 Standardization for generation of arsenic-rich sludge

Arsenic
Volume Arsenic concentration in Bleaching Alum Dry
of raw concentration in supernatant water powder dose dose weight of
water (L) raw water (mg/L) (mg/L) (mg/L) (mg/L) sludge (g)
15 0.51 0.02 5.0 70 0.25335
15 0.53 0.03 5.0 70 0.25305
15 0.52 0.03 5.0 70 0.25335
Table 2 Arsenic concentration in raw water and filtered supernatant water after coprecipitation
Arsenic
concentration Arsenic concentration in supernatant Average removal % of
Sample in raw water water after coprecipitation and arsenic by the method of
name (mg/L) filtration (mg/L) (in %) coprecipitation
ARS-1 0.68 0.045 (93.39) 90.84
ARS-2 0.64 0.055 (91.40)
ARS-3 0.55 0.064 (88.36)
ARS-4 0.50 0.044 (91.20)
ARS-5 0.58 0.058 (90.0)
ARS-6 0.64 0.052 (91.88)
ARS-7 0.68 0.075 (88.97)
ARS-8 0.76 0.078 (89.74)
ARS-9 0.52 0.040 (92.31)
ARS-10 0.54 0.048 (91.11)
15 L bucket water was (0.246 + 0.00705) g, i.e., 0.25305 g. The above process was
repeated several times to generate the arsenic-rich sludge.
Arsenic Concentration in Filtered Supernatant Water After

Coprecipitation
Arsenic-rich sludge was prepared by the process of coprecipitation, utilizing alum

and bleaching powder. The sludge was stored for carrying out study for its safe and
eco-friendly disposal. The arsenic concentrations in raw water as well as filtered
supernatant water for different batch operations are presented in Table 2. Arsenic
was measured by the model AAnalyst 200 Atomic Absorption Spectrophotometer
(AAS) with the model MHS-15 Mercury/Hydride Generation System in the labora-
tory of the School of Water Resources Engineering, Jadavpur University, according
to the standard methods (APHA 2005). The water quality analysis indicated that
90.84% arsenic removal could be possible by the method of coprecipitation. The
percentage of arsenic concentration in supernatant water after coprecipitation
decreased with the decrease in the arsenic concentration in raw water.
Table 3 Arsenic-rich Sample Arsenic concentration in Iron concentration in

sludge analysis name sludge (mg/kg) sludge (mg/kg)
ARS-1 2775 32,250
ARS-2 2550 31,150
ARS-3 2100 36,700
ARS-4 1930 44,474
ARS-5 2290 37,250
ARS-6 2680 35,154
ARS-7 3130 32,197
ARS-8 3250 34,850
ARS-9 2275 35,190
ARS-10 2380 37,198
The arsenic-rich sludge was analyzed for arsenic and iron concentration for
different batch processes. The arsenic concentration in the sludge varied from
1930 to 3250 mg/kg. The iron concentration in the sludge was found to be in the
range 31,150–44,474 mg/kg as presented in Table 3. The arsenic-rich sludge was
digested to solubilize particulate forms to measure total arsenic and oxidize reduced
forms of arsenic and to convert any organic compounds to inorganic ones (APHA
2005). Arsenic and iron were analyzed by using the model Analyst 200 Atomic
Absorption Spectrophotometer (AAS) with model MHS-15 Mercury/Hydride Gen-
eration System in the laboratory.
Preparation of Concrete (M15-1:2:4) with Arsenic-Rich Sludge
Concrete cubes were prepared by using cement, sand and stone chips, and water. In
order to prepare concrete cube, three different sizes of molds, namely, 50 mm,
75 mm, and 100 mm, were used. The specifications of different ingredients of
concrete are furnished below:
• Cement: Ordinary Portland Cement (OPC) of 53 grades conforming to the Indian

Standard Code of practice manufactured by ACC was used in the study.
• Sand: Effective size, 0.28 mm; uniformity coefficient, 2.2; type of sand,
river sand.
• Stone – chips: 18 mm downgrade.
• Water: collected from the Kolkata Municipal Corporation (KMC) tap.
The sludge was added (by weight) in 1%, 0.5%, and 0.1% proportion in M15
concrete preparation. Each of the concrete mixture was placed in three same sizes of
mold, and accordingly nine molds were used for concrete cube preparation. The
concrete cubes were cured for 28 days keeping in water chamber, and compressive
Table 4 Sludge addition in concrete preparation

Water
Sample Sludge Sludge Cement Sand Stone chips added
name conc. (%) added (g) added (g) added (g) added (g) (mL)
ARS-1 1.00 6.65 95 190 380 48
ARS-2 1.00 6.65 95 190 380 48
ARS-3 1.00 6.65 95 190 380 48
ARS-4 0.50 5.50 158 314 628 80
ARS-5 0.50 5.50 158 314 628 80
ARS-6 0.50 5.50 158 314 628 80
ARS-7 0.10 5.65 808 1614 3228 411
ARS-8 0.10 5.65 808 1614 3228 411
ARS-9 0.10 5.65 808 1614 3228 411
strengths were detected for each concrete cube. The details of aggregate and sludge
added for concrete preparation are furnished in Table 4. TCLP testing was carried out
for all concrete cubes.
Use of Arsenic-Rich Sludge in Brick Manufacturing
Nine small bricks were manufactured by using soil and varying proportion of sludge.
The brick dimension was 10.8 5.7 3.2 cm. The soil was collected from Indira
Gandhi Water Treatment Plant, Palta, constructed for laying water pipeline from Palta to
Kolkata city to get treated water. The dried soil in each brick was measured approxi-
mately as 428 g. Dry sludge having arsenic concentration between 1% and 3% was
added with clay to manufacture bricks. Distilled water was used in brick manufacturing.
The brick was sun-dried before burning in muffle furnace at a controlled temperature
and duration. TCLP testing of all the bricks were carried out in the laboratory.
Disposal of Arsenic-Rich Sludge in Anaerobic Bioreactor
Sewage sludge was collected from the activated sludge plant (ASP) located near
Howrah Station (Eastern Railway) for feeding the bioreactor. The sewage sludge was
analyzed in the laboratory, and the characteristics of such sludge have been presented
in Table 5. The physicochemical, chemical, and bacteriological parameters were
analyzed according to the standard methods (APHA 2005). The pH value was
measured by a rugged field kit.
Three bench-scale anaerobic bioreactors made of glass, having a capacity of 5.5 L
each, were installed at the laboratory of the School of Water Resources Engineering,
Jadavpur University, to monitor the stabilization of arsenic-rich sludge by anaerobic
bacteria. Initially all the bioreactors were inoculated by anaerobic bacteria collected from
a septic tank. In each bench-scale anaerobic bioreactor, 5 L of sewage sludge was taken
as feed.
Table 5 Test results for Sl. no. Parameters Results

sewage sample used in
1 pH 6.7
anaerobic bioreactor
2 Total solids (mg/L) 42,660
3 Volatile solids (mg/L) 10,320
4 Volatile acids (as CH3COOH), mg/L 27.3
5 Organic solids (mg/L) 10,186
6 Biochemical oxygen demand (mg/L) 11,442
7 Chemical oxygen demand (mg/L) 20,373
8 Sulfate (as SO4), mg/L 12.5
9 Nitrate as (NO3), mg/L 0.62
10 Iron (as Fe), mg/L 6.4
11 Total coliform (MPN/100 ml) 8 107
12 Fecal coliform (MPN/100 ml) 2.2 107
Arsenic-Rich Sludge Used for Concrete Cubes
Compressive strength for all the concrete cubes was tested in the laboratory, and the
results of such test are furnished in Table 6. The comparative study for compressive
strength indicated except for two samples all the other samples conform to the
standard compressive strength for M15 concrete as per IS 456, 1978. The arsenic-
rich sludge and concrete mixing ratio of 1.0:99, 0.5:99.5, and 0.1:99.9 developed
compressive strength of 15 N/mm2. So, qualitatively the concrete is acceptable for
use. Table 6 indicated that sludge proportion with size of concrete was the key factor
for determining the quality of concrete cubes and bricks. The compressive strengths
of concrete cubes decreased with the increase in sludge proportion.
All the concrete cubes were used for carrying out TCLP test in the laboratory.
The leachate of TCLP tests for the concrete samples was analyzed, and results
are furnished in Table 7. The arsenic content in leachate after TCLP test
indicated that the concentration of arsenic was much below the maximum permis-
sible value as prescribed by EPA (1992), i.e., 5 mg/L. Leachates analyzed for
As indicated presence of arsenic in leachate of concrete cubes ranged between
0.012 and 0.064 mg/L.
Arsenic-Rich Sludge Used in Brick Preparation
The TCLP results highlighted that the arsenic concentrations in leachates of all the
bricks were found to be below the permissible limit (5 mg/L) as per the US-EPA
Standard (see Table 8). Now, as per IS 3102 (1971) and IS 1077 (1992), factory-
made bricks in India have the strength of 17 N/mm2 in dry condition. But common
Table 6 Compressive Sample Sludge in Size of concrete Compressive

strength of concrete cubes name mixture (%) cubes (mm) strength (N/mm2)
ARS-1 1.00 75.0 12.99
ARS-2 1.00 75.0 12.68
ARS-3 1.00 75.0 12.24
ARS-4 0.50 75.0 15.30
ARS-5 0.50 50.0 14.56
ARS-6 0.50 50.0 15.20
ARS-7 0.10 100.0 18.93
ARS-8 0.10 100.0 18.47
ARS-9 0.10 75.0 16.22
Table 7 Arsenic Sample Mixing of sludge (%) in Arsenic concentration

concentration in leachate name concrete (mg/L) in leachate
of concrete cubes after
ARS-1 1.00 0.029
TCLP test
ARS-2 1.00 0.054
ARS-3 1.00 0.045
ARS-4 0.50 0.064
ARS-5 0.50 0.055
ARS-6 0.50 0.039
ARS-7 0.10 0.014
ARS-8 0.10 0.012
ARS-9 0.10 0.016
Table 8 TCLP results for bricks made by using soil and arsenic-rich sludge
TCLP results of
leachate
Sample Dry weight of Dry weight of Comprehensive Arsenic, Iron,
name soil (g) sludge (g) strength (N/mm2) mg/L mg/L
ARS-1 428 4.28 (1%) 3.4 0.0010 0.044
ARS-2 420 5.04 (1.2%) 3.8 0.0012 0.090
ARS-3 425 4.25 (1%) 3.4 0.0010 0.090
ARS-4 427 8.54 (2%) 4.1 0.0034 0.183
ARS-5 424 8.48 (2%) 4.1 0.0025 0.160
ARS-6 425 10.20 (2.4%) 4.9 0.0020 0.150
ARS-7 428 12.84 (3%) 5.2 0.0015 0.150
ARS-8 424 10.6 (2.5%) 5.1 0.0018 0.160
ARS-9 426 12.78 (3%) 5.2 0.0020 Nil
hand-made bricks can have their strength between 3 and 5 N/mm2. Brick samples
were tested, and those brick samples showed strength ranging between 3.4 and
5.2 N/mm2.
Arsenic-Rich Sludge Stabilization in Anaerobic Bioreactor
Initially 370 mL arsenic sludge was added in each of the three anaerobic bioreactors
to mix with 5 L of sewage sludge. The anaerobic bioreactors were sealed properly
keeping an outlet for the release of methane and carbon dioxide gas. The anaerobic
reactor was kept at a warm place (average temperature- 30 C) for 75 days. The
digested sludge samples collected from the bioreactors were analyzed, and the
results are represented in Table 9. Similarly, supernatant liquid of all the three
bioreactors was also analyzed for different parameters which are listed in Table 10.
The anaerobic bioreactor was operated in batch process. Kinetics of sludge
digestion involves two groups of bacteria, namely, acid formers and methane
formers. The digester operated as single-stage reactor and without recirculation.
The hydraulic retention time (HRT) was the same as the solids retention time
(SRT). The volatile solid in the influent sludge of the reactor was measured as
10,320 mg/L (Table 5) indicating volatile solids loading as 10.32 kg/m3/day. It
indicated that thickened sludge was added in the reactor. The volatile acid in the
influent sludge was detected as 27.3 mg/L, and the same was found to be in the range
of 149.37 mg/L and 158.93 mg/L as depicted in Table 10 in the reactors indicating
sludge digestion at lower rate. The volatile solids reductions in the reactors were
observed between 23% and 37% in the reactors observed from Table 9. Normally in
Table 9 Test result for the sludge sample

Results
Sl. no Parameter Bioreactor-1 Bioreactor-2 Bioreactor-3
1 pH 7.20 6.92 7.10
2 Total solid (g) 157.28 146.31 162.36
3 Volatile solid (%) 37.8 22.24 24.50
4 Volatile acid (as acetic acid) (%) 0.437 0.394 0.512
5 Organic solid (%) 15.05 14.74 15.28
6 Arsenic (as As) (%) 0.008 0.007 0.009
7 Aluminum (as Al) (%) 0.545 0.502 0.647
Table 10 Test results for the supernatant sample

Results
Sl. no Parameters Bioreactor-1 Bioreactor-2 Bioreactor-3
1 3 days BOD at 27 C, mg/L 8.53 7.96 8.40
2 COD, mg/L 54.33 49.57 57.54
3 pH 5.81 5.72 5.92
4 Volatile solids, mg/L 51.33 48.64 57.86
5 Volatile acids (as CH3COOH), mg/L 158.93 149.37 155.79
6 Total solids, mg/L 790 740 805
7 Organic solids, mg/L 49.33 41.49 51.00
8 Arsenic (as As), mg/L 0.04 0.03 0.04
9 Aluminum (as Al), mg/L <0.01 <0.01 <0.01
a continuous feed anaerobic reactor, volatile solids reduction could be between 50%
and 60% (CPHEEO 1993).
In the reactor digester, 67.9 mg (370 mL) of arsenic was added with the sludge for
digestion in batch process. After 75 days of digestion period, the arsenic content in
the digester was reduced to 14.75 mg; actually arsenic content in the supernatant of
the digester was analyzed as 0.04 mg/L as shown in Table 10, while arsenic in
digested sludge was found as 80 mg/kg. The batch study revealed that 78.28% (may
be 80%) of arsenic with substrate concentration of 42.66 g/L could get removed due
to arsenic volatilization in the anaerobic bioreactor, whereas substrate concentration
of 25 g/L could volatilize about 35% of arsenic observed by Mahaptra et al. (2008).
In sludge the arsenic remained in As (V) form. The maximum uptake in the reactor
was found to be 1.25 mg As (V) per g of substrate.
The study carried out so far highlighted the following for safe disposal of arsenic-
rich sludge:
(a) The best options for disposal of arsenic-rich sludge could be mixing with
concrete (M15). The sludge could be mixed in 0.1%, 0.5%, and 1% proportion
(by weight) with concrete. The average comprehensive strengths achieved with
the respective sludge proportions are found to be 12.64 N/mm2, 15.02 N/mm2,
and 17.87 N/mm2, respectively. The TCLP test indicated presence of arsenic in
leachate is in much lesser proportion than the permissible limit of the US-EPA
standard (EPA 1992). Banerjee and Chakraborty (2005) found that in the
preparation of briquette, cement-sand mortar and concrete, mixing up to 10%,
18%, and 40% of arsenic-bearing sludge by volume, respectively, with the other
common ingredients did not produce a TCLP leachate beyond its permissible
limit for direct inland water discharge. Also, Banerjee and Chakraborty (2005)
noted that 25% (by volume) of cement could be replaced by fly ash to stabilize
arsenic-laden sludge to the tune of 11% by volume of cement-sand (1:3) mortar.
(b) Mixing of arsenic-rich sludge with concrete (in optimal proportion) would not
reduce the compressive strength of concrete.
(c) The options for disposal of arsenic-rich sludge could be mixing with clay for
manufacturing of bricks. The dry sludge between 1% and 3% could be added
with dry soil. The TCLP results highlighted that the arsenic concentrations in
leachates of all the bricks were much below the permissible limit (5 mg/L) as per
the US-EPA Standard (EPA 1992), and also the brick samples showed strengths
between 4.1 and 5.2 N/mm2, a good point.
(d) Fly ash could be added along with arsenic-rich sludge for preparation of
concrete, but as fly ash may contain arsenic, it would contribute to addition
of arsenic in concrete.
(e) Arsenic-rich sludge could be stabilized by disposing the sludge in an anaerobic
bioreactor. The arsenic-rich sludge could be mixed with sewage sludge for
feeding in anaerobic digester in sewage treatment plant. The total quantum of

arsenic in the bioreactor after anaerobic digestion for 75 days has been estimated
as 14.75 mg of arsenic. The concentration of arsenic in mixed liquid after
anaerobic digestion was calculated as 2.95 mg/L. Thus the calculation revealed
that 78.28% (may be 80%) of arsenic could get stabilized in anaerobic bioreactor.
(f) Arsenic-rich sludge could be stabilized by disposing in anaerobic bioreactor. The
arsenic-rich sludge could be mixed with sewage sludge for feeding in anaerobic
digester in sewage treatment plant.
(g) The arsenic-rich sludge generated in household treatment may be disposed in
household toilet. Alternatively it may also be disposed in biogas plant.
Arsenic removal units (ARU) can be installed as per the following:
(i) Households ARU

(ii) Hand pump attached ARU
(iii) Power pump attached (deep bore well with piped water supply) ARU
The quantum of sludge generation from the abovementioned three types of ARU will
be different. The sludge from household ARU can be disposed in household toilet
having septic tank and soak pit or twin leach pit. Since both the types of toilet are based
on the concept of anaerobic treatment of human excreta, hence arsenic removal through
volatilization could be done if the sludge is disposed in the toilet on a regular basis.
In case of hand pump attached ARU, arsenic-rich sludge can be stored in
underground reservoir. The sludge can be used in the preparation of concrete and
various concrete structures (bench/sitting platform, etc.) that can be constructed
around the ARU. Alternatively the sludge can be mixed with clay during
manufacturing of various types of earthenwares which requires burning between
24 and 48 h in kiln. During burning however arsine gas may be released.
In case of power pump attached ARU, the sludge can be utilized during
manufacturing of concrete paver blocks. In this type of ARU, the quantum of sludge
generation will be higher and will require appropriate method for proper disposal.
Now paver blocks are in great demands in cities and towns for pavement construc-
tion. The paver block manufacturing units can be installed near ARU through local
entrepreneurship for eco-friendly utilization of arsenic-rich sludge.
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Household Hazardous Waste
Quantification, Characterization, 25
and Management in Developing
Countries’ Cities: A Case Study
Waseem M. W. Al-Tamimi, Issam A. Al-Khatib, and

Stamatia Kontogianni
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
Description of the Study Area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
Households’ Sample Size Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
Data Collection Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
HHW Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640
Sample Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641
Solid Waste Management in Hebron City . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
Risk Assessment of Household Hazardous Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
Demographic Factors’ Effect on HHW Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
Hazardous Components of Hebron City Household Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
HHW Recorded Management Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 649
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654
W. M. W. Al-Tamimi
Faculty of Graduate Studies, Birzeit University, Birzeit, West Bank, Palestine
Faculty of Graduate Studies, Birzeit University, Hebron, Palestine
e-mail: w.tamimi_88@hotmail.com
I. A. Al-Khatib (*)
e-mail: ikhatib@birzeit.edu
S. Kontogianni

https://doi.org/10.1007/978-3-319-73645-7_15
636 W. M. W. Al-Tamimi et al.
Abstract
The aim of this research is to assess household hazardous waste (HHW)
management in Hebron city, Palestine, investigating the HHW types and pro-
portions. In parallel the level of awareness of household heads in regard to
knowledge of risks and hazards associated with HHW items is investigated
through a comprehensive survey. Also, analysis of the total generated solid
waste was carried out during a 14-working-day period to detect different HHW
components and their proportions.
Home products constitute the largest percentage of HHW (42.3%), followed
by automotive products (17.2%) and personal care products (15.4%) and
healthcare products (12.3%). Personal care products are the most category of
HHW that is thrown randomly (78.7%).
Socioeconomic factors were related to attitudes and practices of citizens in
regard to HHW. Overall results show the great risk associated with HHW given
that under aged are transferring SW from home to container (40.2%) with high
involved risk of accident; containers in some cases are more than 150 m away
from home (19%) increasing the aforementioned potential risk. In 18.5% of
houses, there was an accident related to HHW risks which are, namely, injuries
(42%), poisoning (36%), burns (22%), etc.
Keywords
Hazardous waste · Household · Management · Separate collection · Survey
Introduction
HHW is the unused, discarded, component of household wastes that contain

chemicals of toxic nature or labeled poisonous, flammable, reactive, explosive, or
corrosive ones. There are different products normally used in households which have
these characteristics, such as pesticides, unused medicines, antifreeze, oil-based
paints, and battery solvents (Bound et al. 2006; Weidenhame et al. 2010;
Kontogianni et al. 2013; Inglezakis and Moustakas 2015; Delgado et al. 2007;
Elston 2010; Court et al. 2015; Couto et al. 2013).
This waste category includes automotive products such as motor oil (which
bears numerous heavy metals, e.g., lead, arsenic, zinc, hydrocarbons, cadmium,
and chromium), fluorescent tubes, electrical equipment, batteries containing heavy
metals (Terazono et al. 2015), waste electronic, wood that had been treated with
hazardous materials, discarded CFC-containing equipment (Slack et al. 2005;
Gu et al. 2014), cleaning products, paint, and pesticides (Kontogianni et al. 2013).
The HHW stream components due to their hazardous toxic characteristics may
adversely affect environment when handling, transferring, or disposing, so they
should be disposed in a special procedure (Hassanvand et al. 2011; USEPA 2005;
Agricultural Research and Cooperative Extension 2014) as well as pollute both
25 Household Hazardous Waste Quantification, Characterization, and. . . 637
surface water and groundwater and in turn wildlife biodiversity. So they should be
collected separately to other domestic waste. The disposal of HHW is and will be
a hot issue for solid waste managers and concerned parties (Wagner et al. 2013).
This way the less we can achieve is to decrease the management difficulties
associated with this type of waste when landfilled, that is, reduce chemical emissions
and leaks to the environment (Fjelsted and Christensen 2007; Kies Strategies et al.
2008; Rosenfeld and Feng 2011). It is confirmed that most of the HHW (80%) will
remain toxic for centuries causing threatening effect and risk of contamination and
land pollution of soil and ground at any time. So proper disposal of HHW is a
necessity for present generation and for future generations (Ortego et al. 1995).
HHW management requires a protocol of actions which include reducing, storing,
collecting, transporting, utilizing, processing, and disposing of toxic and hazardous
waste (Aprilia et al. 2013).
Every household contributes to hazardous waste by some mean or another. There
is still a many of arguments regarding this issue worldwide; how hazardous waste is
produced, how it is collected, and what is its destiny are still a hot issue, and it is
under the spot (Burnley et al. 2007; Duan et al. 2008).
According to EU legislation, certain HHW items belong to this category as
they are “materials resulting from selective waste collections from households and
which exhibit any of the characteristics listed in Annex III” of the Council Directive
on HaW (91/689) bearing properties such as explosive, oxidizing, flammable,
irritant, harmful, toxic, carcinogenic, corrosive, infectious, teratogenic, ecotoxic,
etc. (Kontogianni et al. 2013). There is a wide range of HHW which are not taken
into account when sustainable management programs are implemented (Slack et al.
2004). The latter reveals regulation shortage, so the HHW sustainable management
is still covered by more generic legislation related to hazardous waste. This leads into
HHW following the disposal route of MSW rather than this of hazardous waste
creating, this way, future potential environmental risks and health impacts
(Kontogianni et al. 2013).
Even though HHW is a small fraction compared to the total domestic waste,
the impacts and risks to public health and environmental conditions are severe.
The percentage of HHW varies from country to country, and it also varies in the
same country depending on many factors. But, as a rule of thumb, the percentage
will be between 1% and 4% of the domestic waste. In most countries co-disposal
of MSW with HHW is taking place with all the risks encountered in the long as
well as in the short run. Another source of hazard of the HHW in addition to its
properties is its capability to react with MSW and change it in turn into HHW and
thus duplicating the problem and increasing the threat to the environment (Slack
and Letcher 2011).
As solid and hazardous waste generation increases with population growth and
industrialization, solid waste management (SWM), which broadly encompasses both
urban solid and hazardous waste streams, must deal with problems of waste allevi-
ation, collection, composting, recycling, combustion, and/or final disposal (Kelley
et al. 1989). One or more of these activities may be used in order that best protection
of our environment and society is achieved implementing integrated solid waste

management (ISWM) activities (Fikri et al. 2015). Nevertheless, multidisciplinary
and complex nature of integrated solid waste management challenges makes it
difficult to generate a systematic solution that can cover all aspects of cost, risk,
and future challenge in all times that can be applied in all locations (Wei Lu et al.
2012).
Generation of HHW has grown up more in urban areas which is recognized
by high population growth. This increases the difficulties encountered in handling,
collecting, and final disposal because of the shortage in financial resources,
administrative capacities, infrastructure, as well as necessary equipment. Alarming
increase in MSW with its HHW component associated with the ineffectiveness in
SWM accompanied by change in purchasing habits will make a serious problem and
risk (Otoniel et al. 2008; Ojeda-Benitez et al. 2013; Banerjee et al. 2013).
The citizens are not fully aware of the presence of hazardous and toxic materials
in the domestic waste as well as the involved threat for their health and for the
environment.
One should start solving the issue of HHW through awareness among all citizens.
To this direction campaigns are an appropriate tool toward increasing the public
awareness; society, families, and individuals should know the risks and the threats
associated with such waste on the long and short run. Trends and attitudes should be
driven to change the habits in order to lower consumption of goods containing these
HHW. Factories and industry should adopt this attitude by choosing materials that
have lower HHW and substances that have lower effects on environment. This
change is necessary, although it will not be instantaneous, but it has to begin
(Ojeda-Benitez et al. 2013).
Additionally the future introduction of a sustainable solid waste management
system (SWMS) implementation should take into consideration the hazardous and
toxic components of SW (Aprilia et al. 2013) to make use of the aforementioned
campaign directions presented to citizens.
This study is assessing the current HHW management practices in Hebron city;
through a field study, the generated quantity and quality of the HHW stream
as determined and the knowledge, attitudes, and perception of household heads
concerning the handling of HHW is identified and commented. The latter consti-
tutes the base for the introduction of sustainable waste management system in
the area.
Methodology
Description of the Study Area
Hebron is an old Palestinian city and is located in a governorate carrying its name
Hebron. It lies in the southern region of the West Bank, where Bani Na’im bordered
it from the east, Halhoul bordered it from the north, Taffuh bordered it from the west,
and Yatta to the south (Applied Research Institute 2009). It is located 36 km south of
Jerusalem, and its population was projected to be 195,733 in 2013 (PCBS 2013).
The total area of the city is 45 km2; the number of households was 32,622 in 2013
(Hebron Municipality 2013).
Households’ Sample Size Identification
The sample size was calculated by the equation proposed by Thompson (2012):
N ½ pð 1 pÞ
n ¼
N d2 =z2 þ pð1 pÞ
N: Size of the community

Z: Z-score corresponding to the level of significance equal to 0.95 and 1.96
d: The error rate is equal to 0.05
p: Success rate, taken as 0.50
The size of community equals 195,733, and after substituting in this equation, the
number of household questioners required is 383; the questionnaire was distributed
to 450 households, and 385 respondents finally participated in the research. This
offered a resonance of 85.6% which is considered as a representative percentile for
this research. Analysis of raw data was performed with the application of Statistical
Package for the Social Sciences (SPSS) computer program – version 18. Appropriate
tests of significance using Chi-square test were also performed to find out the
relationship among socioeconomic variables and other dependent variables in addi-
tion to other statistical parameters.
Data Collection Method
Questionnaires were sent to some citizens, and also face-to-face interviews were
conducted to better understand the characteristics of HHW and get reliable answers
from them. The questionnaire consisted of three basic parts: first part was about
demographic and socioeconomic (dependent) variables and diagnostic questions,
second part was about general conditions of SW and HHW collection system
including also practices and trends of citizens in this particular area, and the third
part dealt with individual types of HHW (items) generated and questions regarding
the description of their disposal method followed.
The first part, which is demographic and socioeconomic questions, resembles the
independent variables such as the type of house (separated or apartment), marital status of
respondent, age of housewife, educational level of household owners, employment, the
number of family members, monthly/annual income, and number and age of children.
The second part of questions focuses on general SW issues as condition of
nearby container, sufficiency of container size, possibility that the house contains
hazardous materials related to the employment of parents, location of storing
hazardous materials, responsibility of SW disposal, frequency of waste disposal,

distance of the nearest SW container from home, behavior of children near the SW
container, and indication of accidents that occurred due to hazardous wastes
including both nature and effect of those accidents.
Third part deals specifically with HHW items; the respondents had to identify the
category and specific items belonging to HHW category that are generated at their
houses and also indicate the followed disposal method, e.g., disposal along with
domestic waste, stored for HHW separate disposal, recycling when possible, illegal
disposal.
HHW Classification
Following the field research, an additional 2-month research was conducted to

determine the HHW constituents and proportions within domestic waste. A solid
waste component analysis was carried out during 14-working-day period at Hebron
solid waste transfer station that serves Hebron city during November and
December 2013.
Random representative samples of the disposed household waste at the transfer
station were analyzed. Each day 6–10 samples of 0.5 m3 household wastes were
emptied in a shallow tray band where the solid waste components were categorized
manually by placing them in a pre-weighted and appropriately labeled trays (once
each part has been categorized, it was weighted to record its percentage from the
total household solid waste). The aforementioned was conducted consecutively for
Table 1 Household hazardous waste categories (Delgado et al. 2007)

1 Automotive products (brake fluid, transmission fluid, auto battery, antifreeze, windshield
washer, lotion, motor oil, oil filters, metal polish with solvent, fuel oil, diesel, degreasers,
kerosene, carburetor, cleaner (fuel injectors), and car wax with solvent)
2 Home products (batteries’ button, rechargeable, shoe polish, bleach, aerosol products,
thermometers and thermostats, air fresheners, upholstery, cleaners, fluorescent lights,
ammonia-based cleaners, spot removers/carpet, bleach-based cleaners, disinfectants,
window/glass cleaner, drain cleaner, floor care materials, metallic polish, cleaners for
furniture, furniture polish with solvents, toilet bowl cleaner, smoke detector with solvents
(wax/stripper), cleaners of the oven, pet products, abrasive cleaners or scouring powder)
3 Personal care products isopropyl alcohol (rubbing alcohol), nail polish, hair spray, hair
permanent lotion, hydrogen peroxide, nail polish remover
4 Home improvements latex paint and primer, adhesives and glues (solvent-based), stain and
varnish, furniture stripper, paint and primer, thinner for paint, cleaner from paint on brush,
wood preservative, remover of the paint
5 Healthcare waste medical home products
6 Indoor pesticides rodent poisons and bait, ant/cockroach spray and bait
7 Garden and lawn insecticide, fertilizers including weed killer, fungicides, herbicides, used
pesticide containers
8 Miscellaneous pool chemicals, photographic chemicals (diluted/undiluted), art supplies, and
ammunition
14 days resulting into the formation of 115 samples. Then the samples were analyzed
in terms of manually sorting individual components following the classification
proposed by Delgado et al. (2007). HHW was classified according to eight catego-
ries, as shown in Table 1.
Sample Distribution
Table 2 shows the demographic and socioeconomic characteristics of the surveyed

sample based on the type of the house, house ownership status, marital status of
respondent, educational level, gender, age of house owners, employment, the num-
ber of family members, number and age of children, and total income. About 69.1%
of respondents were living in independent house, and 30.9% were living in
Table 2 Surveyed sample distribution analysis

Independent group Percentages
Type of the house Independent Apartment
house
69.1% 30.9%
Ownership of the house Rented Owned
13.5% 86.5%
Marital status Single Married Divorced
62.3% 36.6% 1.0%
Educational level of Illiteracy Preliminary Preparatory Secondary
respondent certificate certificate
0.8% 13.0% 32.4% 57.0%
Gender Male Female
56.1% 43.9%
Age of housewife Less than 25 26–35 36–45 More than
45
12.9% 26.0% 40.2% 21.0%
Type of work housewife Housewife Working in the Working in
only government the private
sector sector
77.0% 7.4% 15.6%
The number of individuals Less than 5 5–7 More than 7
residing in the home 23.0% 49.5% 27.5%
Presence of children of age Yes No
ranges between 8 months and 59.0% 41.0%
10 years
Monthly income for the family Less than 200–400 JD 400–600 JD More than
200 JD 600 JD
9.8% 26.1% 32.4% 31.6%
apartment. In terms of the house ownership, the highest percentage of respondents

owned their house (86.5%), while the rest were living in a rented house (13.5%).
In terms of marital status, the largest slice of respondents were singles (62.3%),
while divorced constituted the lowest percentage (1%). About 56.1% of respondents
were males and 43.9% were females.
The age distribution was 40.2% in the group 36–45 years old, 26.0% in the
26–35-year-old group, 21.0% in the group older than 45 years old, and 12.9% in
the group less than 25 years old. In general Hebron citizens are relatively young. The
aforementioned is considered to be a privilege for educating and awareness since
they are usually willing to contribute in changing to sustainable conditions.
The highest percentages of respondents (57.0%) in terms of level of education were
those who have a Secondary Certificate, while illiteracy is very low (0.8%).This is a
good indicator about the level of education of the society; education and awareness
campaigns are easily and efficiently conducted, and their results are of high quality
since the issued leaflets and bulletin can be read by almost all addressed citizens.
The highest percentage of respondents (59.0%) was parents and their children
between 8 months and 10 years. This introduces a high-risk indicator associated with
children injuries occurring from HHW. Palestine in general has a high percentage of
children compared to other developed countries. Shortage of awareness regarding
the HHW and its involved risks combined with shortage of playgrounds and kids’
clubs increases hazard risk; the children play in unprotected areas, e.g., household
surrounding areas possibly near containers where injuries from HHW presence are
frequent.
Regarding the level of income, the largest percentage (32.4%) consisted of those
whose family has a monthly income of 400–600 JD, and the lowest percentage
(31.6%) was of those whose monthly family income exceeds 600 JD. As the figures
show, only one-third of the sample has an income more than 600 JD (i.e.,
1 JD = 1.41 USD). Almost two-thirds of the population is low incomed, and this
usually results into high vulnerability to risks due to less information dissemination
and insufficient follow-up procedures proposed in organized campaigns.
Solid Waste Management in Hebron City
The results of Fig. 1 show that the responsibility of SW disposal is 36.3% by the
head of the house, compared with 40.2% responsibility by the children and 9.5% by
the housewife. Hazard risk is introduced in this action since if children are not aware
of how to deal with the SW in case of sack tearing or any other scenario, then they
may be injured and/or exposed to diseases affecting their health. The aforementioned
concerns injuries by needles, exposure to chemicals, hauling toxic materials, etc.
Directions and guidance of children are crucial parameters which must be taken into
consideration.
Figure 2 shows that 61.4% of the households in Hebron city are disposing SW
every day, and 24.9% of the households are disposing them every 2 days. Regular
SW disposal decreases the possibility of home storage and decreases the risks
Fig. 1 Responsible person All

for transferring garbage from 12.6%
home to container Building guard
1.4%
Householder
36.3%
Children
40.2%
Housewife
9.5%
Fig. 2 The disposal of solid When there is a

Every week
waste from home to container need
4%
1%
Every three days
8%
Every two days

25% Every day
62%
Fig. 3 The distance of the There is no

nearest solid container from container
More than 150
the house 8%
meters
11%
Less than 75
meters
76-150 meters 53%
28%
associated with HHW injuries. The introduced risk of SW home storage stands for
14% of the population.
Figure 3 shows that 53% of the households in Hebron city are at a distance of less
than 75 m from the nearest solid waste container, compared with 28% of the homes
at a distance from 76 to 150 m and 8% having no container nearest to the household.

It is a fact that 8% have no container nearby and thus are carrying their garbage to a
very far site away from their home, or they are disposing them illegally (burning
them in their yards or throwing it randomly on the street). This introduces high risks
to those family members as well as their neighbors associated with both SW and
HHW hazard.
Risk Assessment of Household Hazardous Waste
To investigate the risks of HHW, the anticipated health and environmental problem,
and the relationship between HHW and citizens’ practices in this field, residents were
requested to reply to a set of questions shown in Table 3.
In Hebron city nearly 8.8% of the houses contain hazardous materials which are
related to the employment of the parents. This is a non-negligible percentage since if
the house always contains such materials, at any time there is high probability of
an accident occurrence. Awareness rising will activate parents into keeping
these materials away from children, handling them with caution even when they
dispose them, and also teaching their children about the hazard introduced from
those materials. Another risk is introduced if children are playing near the SW
container and is calculated to be 27.2% since they may bear infectious, explosive,
etc. elements threatening their health. 18.5% of the investigated families included a
member who suffered from a HHW accident. This percentage could be less if the
citizens were aware of the hazardous effects and were encouraged to follow safety
measures during those item handling. Most of the families have at least one child in a
family (59.0%) which constitutes a motivation factor for paying the required atten-
tion in this field. In 35.6% of the cases where one member of the family had been
injured or disposed to HHW, negative psychological effects were noticed for a long
period of time. The cost of applying preventive measures to prohibit HHW accidents
is less than cost of treating the effects of the anticipated accidents on the long and
short run.
In case that a HHW accident had occurred, Fig. 4 shows that 57% of the
households started to keep hazardous materials in a safe place after the accident
occurrence, compared to a percentage of 26% who are no longer storing hazardous
Table 3 Diagnostic results for risk assessment

Percentage
Risk factor (%)
The house contains hazardous materials related to the work of the parents 8.8
Children play with solid waste in nearby containers 27.2
One of the family members had suffered from accident because of hazardous 18.5
household waste
Presence of children of age ranges between 8 months and 10 years in the house 59.0
There is negative psychological effect on infected person from HHW 35.6
Fig. 4 Keeping and storage

of hazardous waste materials Not-stored in the No change
house 17%
26%
Kept in a safe place

57%
material in their homes. But there is a remarkable percentage of 17% who did not
take any action after the accident. This is the category of citizens who should be
awakened to be aware of the potential hazard that they and their children are
exposed to.
The adverse effects of HHW may not be immediately spotted, but many types of
HHW can cause injuries, burns, and poisoning. The types of accidents associated
with hazardous waste in Hebron city as recorded in the frame of this survey are 42%
injuries, 36% poisoning, and 22% burns. The highest percentage occurred due to
sharp items. The introduced risk is doubled when infectious items exist since they
may contaminate all household members with diseases such as HIV, etc.
Demographic Factors’ Effect on HHW Management
In order to see the effect of different demographic factors on the trend, behavior, and
attitude of citizens toward HHW, cross tabulation was carried out between dependent
(practice and behavior) and independent (demographic) parameters. If the p-value of
the test is less than 0.05, then there is a statistically significant relationship between
the parameters.
As shown in Table 4, there is a statistically significant relationship regarding
willingness to separate HHW into different components and placed into colored
sacks between single and married citizens. The overall percentage of citizens willing
to separate is 64%; singles constitute 60% and married 73%. Perhaps married
individuals are committed in those activities more than singles due to the existence
of children in the household or the potential of having one in the future. This is a
clear indicator of the required efforts in raising the awareness of singles compared to
married ones.
It is interesting to note the strong statistical relationship between the number of
family members and the possibility of HHW accident as shown in Table 5. The
overall percentage of occurrence of HHW accident is 18% and only 10% for five-
member families and 26% for five- to seven-member families. Dramatically, this
Table 4 Cross tabulation between marital status and willing to separate HHW into specific
fractions
Marital status Yes for free (%) Yes for a small payment (%) No (%)
Single 60 16 24
Married 73 9 19
Divorced 0 25 75
Total 64 13 23
Chi-square = 14.552, df = 4, p-value = 0.006
Table 5 Cross tabulation between the number of family members and occurrence of HHW
accident
Occurrence of HHW accident
Number of family members Yes (%) No (%)
Less than 5 10 90
5–7 14 86
More than 7 34 66
Total 18 82
Chi-square = 22.483, df = 2, p-value = 0.000
percentage increases to 34% for family of more than seven members. Larger families
usually create higher-level responsibility for parents, and since time is limited, little
attention is given to measure taking or teaching children regarding the adverse
effects of HHW. To overturn this, great attention must be given to all family
members, and they must raise their awareness for HHW through informational
campaigns.
Hazardous Components of Hebron City Household Waste
Total quantity of analyzed SW in this study was 14,562.1 kg out of which

140.669 kg was HHW; the average percentage is 0.97%. Table 6 shows the amount
of household solid waste in the years 2011 and 2014. The estimated values in 2014
are based on the population (estimated by the PCBS for the West Bank and Gaza in
2011 and 2014). The HHW quantities in the Palestinian territories in the year 2014
were estimated as 0.97% of the household solid waste, reaching 22.78 t/day.
Table 7 presents a list of HHW generation research results. The HHW generation
rate (g/person/day) in Palestine was significantly higher than other regions in terms
of generation amount with the exception of Hong Kong and Suzhou, China. In terms
of the proportion of HSW, Hebron city is in the intermediate among other cities/
countries. Some differences were very large. For instance, orders of magnitude
differences in the generation amount were found among Palestine; Suzhou, China;
Hong Kong; and the Mekong Delta of Vietnam. The differences in HHW yield
among various regions and countries can be explained in numerous ways. For
example, in China and according to Gu et al. (2014), the high rate of HHW
Table 6 Average daily quantity of household solid waste produced in the Palestinian territory in
2011 and 2014 and HHW in 2014
Daily HHW
Daily SW Daily SW HHW generation
generated generated generated rate
Population Population in 2011a in 2014b in 2014 (g/person/
Region 2011 2014 (ton) (ton) (ton) day)
Palestine 4,168,860 4,550,368 2151.9 2348.8 22.78 5.0
territory
The West 2,580,168 2,790,331 1505.4 1628.0 15.79 5.7
Bank
Gaza 1,588,692 1,760,037 646.5 716.34 6.948 3.9
Strip
a
PCBS: Household Environmental Survey 2011
b
Estimated based on the population growth rate
Table 7 HHW concentration reports

HHW generation, Share of HHW to household
Country and/or city g/person/day solid waste (%) References
Austria 3.84 – Yasuda and
Tanaka (2006)
Cuitzeo Basin, 1.01 1.03 Delgado et al.
Mexico (2007)
Palestine 3.9–5.7 0.97 Present study
Hong Kong 6.03 0.70 Edwin (1997)
Germany 0.92 6.03 Gu et al. (2014)
Japan 5.48 0.25–0.40 Yasuda and
Tanaka (2006)
Mekong Delta, 0.53 0.20 Thanh et al.
Vietnam (2010)
Suzhou, China 6.16 2.23 Gu et al. (2014)
Tulsipur, Nepal 3.30 1.00 Dangia et al.
(2013)
Vienna, Austria 2.66 n/a Gu et al. (2014)
Municipality of 1.038 Kontogianni
Kalamaria, Greece et al. (2013)
generation may stem from Chinese consumers’ behavior in generating waste (Wei
2012). Many unused products were in the Chinese domestic waste contributing
approximately 10% to PC, far more than the assumption of less than 5% made by
Delgado et al. (2007). In addition, most “Made in China” consumed products were
contributed higher than expected levels of hazardous substances to PC (Zhao et al.
2009). Furthermore, HHW has undergone significant changes corresponding to
urbanization and fast economic growth (Duan et al. 2008; Otoniel et al. 2008).
The statistical parameters of the different components of HHW are shown in
Table 8. The larger coefficient of variation (standard deviation divided by mean) is
for lawn and garden as expected with a value of 7.7. The lower one is for home
products (0.6) as there is stability and similarity in this percentage among different
households. The same applies for the personal care products whose percentage is
(0.9) and to some extent to healthcare waste (1.1).
Results in Fig. 5 show that the home products are the largest component of HHW
with a percentage of 42.3%. Most of the HHW are usually home products like
batteries, cleaners, and others not classified under any specific category. Automotive
products come in the second rank with a percentage of 17.2% since most of the
households have one car or more. The personal care products come in the third rank
Table 8 Percentage distribution of household hazardous and nonhazardous waste components in

Hebron city
Statistical parameter
Coefficient
Waste component Min % Max % Mean % SD of variation
Automotive products 0.0 3.228 0.191 0.428 2.2
Home products 0.0 1.196 0.411 0.245 0.6
Personal care 0.0 0.682 0.148 0.135 0.9
Home improvements 0.0 1.197 0.072 0.169 2.4
Healthcare waste 0.0 0.656 0.122 0.131 1.1
Indoor pesticides 0.0 0.238 0.006 0.035 5.4
Lawn and garden 0.0 0.111 0.002 0.012 7.7
Miscellaneous 0.0 0.659 0.052 0.124 2.4
Nonhazardous 96.32 99.870 98.996 0.636 0.0
household waste
50.0%
42.3%
40.0%
30.0%
20.0% 17.2%
15.4%
12.3%
10.0% 7.0%
5.0%
0.7% 0.2%
0.0%
Fig. 5 Percentage of HHW components by weight from 0.97%

with a percentage of 15.4%. The lowest percentage is the products for lawn and
gardens with a percentage of only 0.2%. The high percentage of healthcare waste
(12.3%) is alarming since their components are potentially toxic on soil, water, and
air since extra or expire date drugs are often disposed with domestic waste.
In a study carried out in Mexicali city, the cleaning product waste was the largest
component of HHW with a percentage of 43.89% (Benitez et al. 2013). In our study
cleaning products were only one part of the home products, which have a percentage
of 41.1% which is close to that of Mexicali, assuming that the major part of HHW
home products is cleaning materials. In Mexicali city, the study of the second
component in rank was about personal grooming aids and beauty products with a
percentage of 23.30%, while this component was the third one in rank in our study
with a percentage of 15.4%. Again, the type and percentage of waste components
reflects the culture, attitudes, practices, and ideology of a community. It may be
possible to some extent to analyze the culture and development of a community by
analyzing their solid waste.
In Malaysia, the higher-income group had the larger generation rate of municipal
solid waste. This is a result of the higher affordability of purchasing and thus
consuming more ready-made goods. Alternatively, the lower-income group also
had larger amount of generated municipal solid waste; this is because this group
tends to produce their own needs, causing production of by-products and wastes.
The average hazardous household waste was 1.76%, which is more than the case of
Hebron (1%). In Malaysia the generation per household ranges from 5.94 kg/day for
low-income families to 7.02 kg/day for high-income families. The corresponding
percentages of HHW in the generated MSW are 1.46% and 1.8% (Fauzia and
Agamuthu 2013; Fauziah and Agamuthu 2015). The medium-income families
generate 3.51 kg/day MSW (1.03% HHW).
Although medium-income category produces the lowest amount of MSW, the
existence of hazardous component was in the range of 2% which is 0.07 kg/
household/day. The high- and low-income groups were generating 0.13 kg and
0.09 kg/household/day, respectively. This generation rate is larger than that of the
medium-income category. No significant differences in the amount of HW were
detected (Fauziah and Agamuthu 2015).
On the other hand in municipality of Kalamaria, Greece, the group of house
owners, namely, “medium income and high education,” present the greater popula-
tion into the survey sample, and ultimately they generate the larger HHW quantity as
well as greater MSW quantity in general. Here it must be mentioned that this type of
household items, coming from categories such as “paint and varnishes,” “containing
CFC,” and “wood preservatives,” constituted also the greater fraction out of all
investigated HHW groups (Kontogianni et al. 2013).
HHW Recorded Management Conditions
Through the questionnaire the disposal method of HHW was investigated. Forty-six
HHW items were covered by the questionnaire separated into four major categories
(automotive products, home products, home improvement products, personal care

products). Results are presented in Table 9.
Disposal method of HHW included disposal with other domestic waste, storage
in household for separate collection, recycling, and illegal disposal. Analysis of
methods of management of HHW was carried out in relation to the category of
the HHW (home, automotive, personal care, and home improvement) as shown in
Table 10. Automotive products on average are disposed with 40.9% domestic
waste, 30.9% of them are stored for separate collection, 12.1% are recycled, and
16.1% are illegally disposed. The replies prove the existent bad practices
followed. In Table 11 it is evident that the home products are 73.0% disposed
with domestic wastes, 12.4% stored for separate collection, 6.1% recycled, and
8.5% illegally disposed. Table 12 shows that personal care products are mostly
(78.7%) disposed with domestic wastes which are similar at some point to that of
home products, 7.0% stored for separate collection, 5.4% are recycled, and 8.9%
are illegally disposed. The results are raising questions regarding the source
Table 9 Disposal of Category of HHW product No. of questionable items

HHW items as
Automotive products 13
recorded through
questionnaire Home products 20
responses Home improvement products 6
Personal care products 7
Total 46
Table 10 Percentage distribution of methods of management of HHW automotive products

Management method
Disposed with the Stored for Illegal
HHW item domestic wastes separate collection Recycle disposal
Antifreeze 50.0 24.1 6.5 19.4
Auto battery 21.5 39.8 17.2 21.5
Automatic transmission 33.7 35.9 12.0 18.5
fluid and motor oil
Brake fluid 50.0 29.5 8.9 11.6
Carburetor cleaner (fuel 27.9 36.1 16.4 19.7
injectors)
Car wax with solvent 50.0 29.5 8.9 11.6
Degreasers 22.4 43.3 9.0 25.4
Diesel 34.5 32.2 12.6 20.7
Fuel oil 45.5 30.7 10.2 13.6
Kerosene 51.6 17.3 22.7 8.4
Metal polish with solvent 56.7 22.8 10.2 10.2
Oil filters 31.3 42.2 10.9 15.6
Windshield washer 57.1 18.5 11.9 12.5
solution
Average 40.9 30.9 12.1 16.1
Table 11 Percentage distribution of methods of management of HHW home products

Management method
Disposed with Stored for
the domestic separate Illegal
HHW home product item wastes collection Recycle disposal
Air freshener 75.7 9.0 5.1 10.2
Batteries – button, rechargeable 75.7 10.0 3.4 10.9
Bleach 80.7 7.7 6.2 5.3
Cleaner – all purpose 77.8 10.8 6.1 5.4
House cleaner – ammonia-based 66.9 16.2 6.6 10.3
Cleaner – bleach-based 81.5 9.1 3.5 5.9
Disinfectant 75.8 11.8 5.5 7.0
Drain cleaner 68.9 18.1 5.2 7.8
Floor care products (wax/stripper) 75.9 12.6 5.8 5.8
Fluorescent lights 76.7 9.4 2.8 11.1
Furniture polish with solvents and 74.7 9.7 7.3 8.3
furniture cleaner
Oven cleaner (lye based) 78.6 11.8 2.6 7.0
Pet supplies/flea and tick control 43.5 27.2 12.0 17.4
Scouring powder or abrasive 80.2 7.0 7.6 5.2
cleaners
Shoe polish 80.3 7.2 3.9 8.6
Smoke detector 42.4 30.3 9.1 18.2
Spot removers/carpet and 67.6 16.6 7.6 8.3
upholstery and rug cleaner
Thermometers and thermostats 74.3 9.9 9.6 6.2
Toilet bowl cleaner 83.1 7.8 3.9 5.3
Window/glass cleaner 78.7 6.7 7.8 6.7
Average 73.0 12.4 6.1 8.5
Table 12 Percentage distribution of methods of management of HHW personal care products

Management method
HHW personal care Disposed with the Stored for Illegal
products item domestic wastes separate collection Recycle disposal
Hair spray 77.3 7.0 5.6 10.1
Hair permanent lotion 76.4 7.2 5.3 11.0
Hydrogen peroxide 77.0 9.7 6.1 7.3
Isopropyl alcohol 77.6 6.2 8.1 8.1
(rubbing alcohol)
Nail polish 81.7 6.7 3.2 8.3
Nail polish remover 82.4 4.9 4.3 8.3
Average 78.7 7.0 5.4 8.9
Table 13 Percentage distribution of methods of management of HHW home improvement

products
Management method
HHW home Disposed with the Stored for Illegal
improvement product items domestic wastes separate collection Recycle disposal
Adhesives and glues 79.3 9.3 2.6 8.9
(solvent-based)
Oil-based paint and primer 69.3 16.8 5.1 8.8
Paint brush cleaner 64.0 17.6 8.8 9.6
Paint remover and stripper 60.9 21.7 7.8 9.6
Paint thinner 61.8 17.4 9.0 11.8
Wood preservative 54.8 22.6 9.5 13.1
Average 65.0 17.6 7.1 10.3
Table 14 Percentage distribution of methods of management of HHW in relation to their category

Management method
Disposed with the Stored for separate Illegal
HHW categories domestic wastes collection Recycle disposal
Automotive 40.9% 30.9% 12.1% 16.1%
products
Home products 73.0% 12.4% 6.1% 8.5%
Personal care 78.7% 7.0% 5.4% 8.9%
products
Home improvement 65.0% 17.6% 7.1% 10.3%
products
separation program effectiveness in the area. Table 13 shows that for HHW items
related to home improvement products, the disposing method is 65.0% disposal with
domestic wastes, 17.6% storage for separate HHW collection, 7.1% for recycling,
and 10.3% illegal dumping.
Table 14 summarizes the management methods of HHW in relation to their
category. It was expected by researchers that personal care product is the category
that is mostly disposed with domestic wastes (78.7%). Automotive products have the
highest percentage (as expected) of recycling (12.1%), although this is not a satis-
fying result, but they also have the highest percentage of storage for HHW collection
(30.9%) and also unfortunately the highest percentage being thrown randomly.
To meet the challenges of the introduced risk associated with HHW, organized
awareness strategy should be adopted and implemented. Intervention and innovation
solutions should be adopted; among these may be separation of HHW at source and
cooperation with private sector for economical reuse or recycle of HHW. Further
studies on the issue of HHW should be carried out to focus on this subject that is
neglected most of the time and in most places. Studies should cover the HHW
accidents, detailed effect of citizens’ habits, and demographic conditions on their
practice and behavior toward HHW and to detect differences due to geographic and
urbanization variations.
The study contributed largely to the identification of the HHW fraction through
the field research performed. The research consisted of two parts: the first in regard to
components of HHW in Hebron and it was carried out by analyzing the waste in the
transfer station. The second part concerned the trends, practices, and attitudes of
citizens in regard to HHW management and the effect of demographic parameters on
these issues. This was carried out using a questionnaire that was analyzed for
385 respondents.
The study showed there were some negative practices that may affect health of
citizens especially children since they are partly responsible for transferring SW
from home to container in 40.2% of the cases. In most cases the container is less than
150 m from home with 81%, but for 19% either it is far or there is no container at all.
This is an alarming fact that should be pursued by local SW collection service.
Risks associated with HHW were examined in order to diagnose any hazard source.
In 8.8% of households, there is a hazardous substance stored, which relates to parents’
employment. In 27.2% of houses, the children are playing close to the nearby container,
a fact that the responsible authorities should work on and provide sites and activities for
children to invest their time properly. In 18.5% of houses, an accident occurred due to
HHW. This is considered as a high percentage in the field of health and safety, and
responsible individuals, institutes, and local and governmental authorities must take
immediate steps and disseminate information and best practices for HHW management
before any severe accident occurrence. The study revealed that individuals exposed to
HHW accident suffer psychologically for a long time from accident in 35.6% of cases.
The accidents usually include injuries (42%), poisoning (36%), and burns (22%).
The hazard risk is high compared to the percentage of HHW in domestic waste
which is approximately 1%: home products constitute the largest percentage of
HHW (42.3%), followed by automotive products (17.2%), personal care products
(15.4%), and healthcare waste (12.3%). The least contribution was by the lawn and
garden product category (0.2%) followed by indoor pesticides (0.7%), which
indicates the low attention paid to home gardens and home agriculture by the
citizens. This is partly owned to the fact that they are mostly low-income citizens
who are mainly focused on making a living for them and their children instead of
outdoor hobbies (preferred mainly in developed countries).
The study diagnosed the current practices of citizens in regard to HHW
management. Personal care products are the most categories which are disposed with
domestic waste (78.7%), while automotive products are the least (40.9%). Automotive
products are the most that are saved for HHW collection (30.9%) and also for recycle
(12.1%) and also have the highest percentage of being thrown randomly (16.1%).
Awareness and education in the field of SW and particularly HHW should be
given a priority. Awareness should be based on a parent-children strategy and
designed by responsible personnel who not only take into account the properties
of this waste fraction but also have background knowledge of the different behaviors
and attitudes of people as formatted by their socioeconomic status. Each citizen
category should be targeted with a separate suitable approach. At the same time, the
campaign participants may include higher institutional level personnel, e.g., local
councils, NGOs, and concerned governmental authorities.
Awareness should be implemented through the use of various means like
bulletins, leaflets, brochures, internet, radio, TV, etc., and focus primarily on
low-consumption concept, promoting the concept of waste minimization.
SW collection service efficiency should be improved horizontally to achieve for
the maximum collection coverage and ultimately sustainable waste management.
The aforementioned includes efficiency in collection frequency, setting of waste
containers in all neighborhoods, availability of the necessary number of collection
vehicles, etc. Those actions will certainly back up the recommended alternatives
such as the sustainable organization of HHW separate collection system and stabilize
the sorting range recorded in this field research (i.e., 7–30.9%) for all households.
Communication of the importance and introduced risk out of this waste fraction is
also another backup parameter. There should be also promoted the idea of recycling
or reusing of certain HHW. This challenge can be achieved through close coopera-
tion with private sector: implementation of investments to make use of HHW
creating also job opportunities and promoting circular economy concept.
Further studies should be carried out to affirm the HHW fraction percentage
in Palestine. The main parameters of those studies besides the actual quantity and
quality of this fraction are still the number of accidents due to HHW, the long-term
and short-term effects, and the indicated variations due to the specific geographic
and socioeconomic factors.
Cross-References

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Investigation of the Chemical Content
of Two Specific Streams in Municipal 26
Waste: The Case of Hazardous
Household Waste and Dental Waste
Stamatia Kontogianni, Nicolas Moussiopoulos, and

Issam A. Al-Khatib
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659
Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659
Waste Streams Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659
Current Management Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661
Material and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663
Determination of the Xenobiotic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663
Development of Databases and Linkage to the Population Target Group . . . . . . . . . . . . . . . . . 664
Uncertainty Level Assessment for Both Fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
Health and Safety in Solid Waste Management Facilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
Hazard Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
Uncertainty Analysis Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
Chemical Compound Properties in Determined Microenvironments . . . . . . . . . . . . . . . . . . . . . . 668
Health and Safety Condition Influence due to Chemical Compounds Contained in
Investigated Waste Fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
Hazard Assessment of Waste Fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
Hazardous Household Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
Dental Waste Fraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 673
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
S. Kontogianni (*) · N. Moussiopoulos

I. A. Al-Khatib
e-mail: ikhatib@birzeit.edu

https://doi.org/10.1007/978-3-319-73645-7_16
658 S. Kontogianni et al.
Abstract
A variety of chemicals is included in the household hazardous waste and the
dental waste fractions that are sadly both parts of municipal solid waste in Greece.
These chemical compounds have hazardous properties according to international
and European regulations.
In Greece, the categorization of household hazardous waste is not indicated
by any legislation, whereas for dental waste the legislation is existent since
May 2012, but the development of a management plan undertaken by the
Hellenic Dental Association is not yet active. Given that both waste fractions
are managed with other municipal solid wastes, they are spotted in solid waste
management facilities causing multiple impacts and challenging the labors’
health and safety status.
Desk research involving literature and commercial research was conducted in
order for the hazardous substances of each of the aforementioned waste stream to
be pinpointed; collected data were compiled into databases for those two specific
waste streams and were categorized based on their hazardous properties and the
waste facility they are most likely to be found in. Parallel field researches were
conducted to: (i) determine the uncertainty level of the fractions, composition,
and health/environmental impacts, and (ii) specific parameters were introduced to
determine their impact due to the status of health and safety conditions within the
management facilities in Greece. Despite the fact that HHW is almost 10% of the
total MSW, it was found that 4.00% of their compounds involve a toxic risk and
7.16% of them involve combination risks for humans working in treatment
facilities; ten chemical compounds, which are included in this fraction, are
categorized as R39/23/24/25 (toxic). On the other hand, in DW, 8.82% of the
included chemical compounds involve a toxic risk and 11.76% of them involve
combination risks for humans.
The qualitative and quantitative analysis of those waste fractions presented in
this paper will pave the way toward organization of both waste streams’ man-
agement plan followed by compiled strategies and recommendations to divert
them from the municipal waste stream and lead them to safe and sustainable
management paths.
Keywords
Hazardousness · Municipal waste · Waste management facilities · Chemical
content · Chemical compounds · Risk level · Uncertainty · Scenarios
Abbreviations
AMS Alternative management systems
DW Dental waste
HHW Household hazardous waste
mE Microenvironments
MRFs Mechanical recycling facilities
MSW Municipal solid waste
SWM Solid waste management
26 Investigation of the Chemical Content of Two Specific Streams in. . . 659
Introduction
Municipal solid wastes (MSWs) are constituted by a variety of waste fractions and
result from various sources which include households, commercial activities, gar-
dens, electric and electrical equipment, private doctors’ consulting rooms, etc. Some
of these fractions include chemical compounds, which based on the European Waste
Catalogue have hazardous characteristics, such as flammable, toxic, harmful, corro-
sive, irritant, oxidizing, etc. For some of the aforementioned MSWs such as wastes
from electric and electrical equipment, batteries, etc., alternative management sys-
tems (AMS) are active in Greece, whereas for others such systems do not exist.
Well-established substances, particularly organic chemicals, are less likely to have had
to conform to tests for hazardous properties, although many are currently being assessed
in light of evidence from long-standing use. It has been estimated that less than 2% of the
30,000–100,000 synthetic (manufactured or extracted) chemicals available today have
been tested for toxicity and even fewer for long-term effects (Slack et al. 2009).
Since their toxicity is evident by the moment they are disposed to the municipal
bins until their transportation to transfer stations or mechanical recycling facilities
(MRFs) or to sanitary landfills, a close identification and research of their chemical
content is required for the benefit of both environment and human health. The
present paper focuses on two waste streams, which bear the aforementioned char-
acteristics: hazardous household waste (HHW) and dental waste (DW). The specific
targets of the conducted research were the following:
• Determination of waste streams according to international and European

standards
• Recording of their quality and the determination of chemical compounds from the
generation point to the final disposal
• Determination of the hazard risk level as individual waste streams as well as
components of the MSW
The potential hazards, which are analyzed, are related to the following:
• Products and chemical composition

• Facilities and the followed management route once they are disposed as waste
• Health and safety status of the facilities’ labors, citizens, and urban environment
• Risks related to their presence and their interaction with MSW
Background
Waste Streams Description
Hazardous Household Waste

HHW quantity based on European field researches and Hellenic reports including
estimations is low, whereas their chemical content is of great importance for the
environmental and health sustainability according to international organizations.
According to Wolf et al. (1997), it was found that the consumers actually consume
62% of paint product content, 89% of pesticide product content, 90% of cleaning
product content, and only 46% of the automobile product content. The remaining
content of the products of each category is disposed along with the packaging in
order to be managed.
The basic categories of HHW are (Gurski 1995; Kontogianni et al. 2013;
Inglezakis and Moustakas 2015) the following:
• Batteries and accumulators

• Craft and laboratory products (e.g., paints and varnishes, wood preservatives)
• Garden care products (e.g., insecticides, fertilizers, etc.)
• Personal care products
• Cleaning products
• Containing chlorofluorocarbon (CFC)
• Medical products and devices containing mercury
• Automobile products
Perhaps some of the individual end-of-life products (constituting HHW) can be

classified into more than one category presented above or combined to form a more
analytical list of categories. However, the main purpose of the research was to create
a coherent classification to ease the overall description of the HHW fraction. To
achieve this, the products involved in the research had to be determined. The great
scale of the HHW fraction may lead into wrong perceptions of what is included in
this fraction. The products, which fulfill the following parameters, were the ones that
were included into the overall research and constitute the HHW fraction:
• They belong to a wide consumer range (e.g., products with high consumption).
• They are products used in households and not for professional or industrial use.
• Their end of life is followed by waste disposal (package and remaining content),
not by refill.
• No organized AMS exists for their collection and treatment and they are managed
with the MSW.
The categories involved in this desk research resulted to be (a) craft and labora-
tory products, (b) garden care products, (c) cleaning products, and (d) mercury-
containing medical devices.
Dental Waste
DWs include any product used or any item generated by a dental unit due to patient
care (treatment and/or restoration) including amalgam, saliva, etc. Dentists restrain
from the use of amalgam, and they have partly replaced it with dental resins in new
dental restorations, but the removal of old restorations will continue to generate
amalgam waste, which contains mercury (Kim et al. 2016).
DWs involve a wide range of waste products in which the biological hazard is
dominant. Yet their chemical content is also of significant concern even though it has
not been thoroughly investigated. The waste categories include waste packages and
product remaining from treatment or diagnosis activities such as (Ferraris et al. 1999)
X-ray, infection control, tooth fillings, pharmaceutical products, prosthetic dentistry
products, and cleaning products. Some of the chemical contents have been targeted
for causing allergic reactions to patients and being ecotoxic.
The aforementioned groups of products were involved in the overall research
aiming to pinpoint the chemical identity of the fraction. The individual products had
to fulfill the following parameters:
• They constitute exclusively dental materials/products approved by the National

Medical Association.
• Their end of life is followed by waste disposal (package and remaining content),
not by refill.
• They are disposed as solid waste in the waste bin of the dental unit (not in dental
technician’s office or in the households) and not in sewage.
Current Management Trends
Hazardous Household Waste Stream

Worldwide HHW management initiatives have been undertaken by municipal,
governmental, or environmental organizations. In most countries, though HHW is
not considered a hazardous fraction worthy of separate treatment, they are landfilled
along with all MSW generated or they are recycled in MRFs since their packaging is
usually recyclable. This remark raises worries regarding the chemical compounds’
impact to workers of MRF where the content of the recycling bins is heading
(Kontogianni and Moussiopoulos 2017).
During an info day on recycling issues, in the frame of the international project
Zero Waste (MED 2012) (where the outcomes of a field research on recycling were
presented), scientists came to the conclusion that a significant percentile of the
citizens (who are actively participating in recycling procedures) did not know or
did not follow the proper recycling rules, e.g., cleaning of the product packages prior
to their disposal in recycling bins. This remark also raised worries regarding the
chemical compound’s impact to workers of MRF where the content of the recycling
bins is heading.
Based on the available data for annual HHW generation per capita, the average
value and standard deviation is 3.23 1.71 kg/inh (26 values in total, range
0.4–7.9 kg/inh). There is considerable scattering of values, as expected, due to the
different collection methods and management schemes used in different countries. In
terms of annual HHW collection per capita in Europe, the average is 2.18 1.20 kg/inh
(11 values, range 0.97–5.2 kg/inh). The quantities of HHW separately collected in
EU range between 1.3 and 5.2 kg/inh/year depending on the country and the
collection method used (Inglezakis and Moustakas 2015).
In China, on the other hand (Gu et al. 2014), research results indicate that the rate
of HHW generation was 6.16 (0.16–31.74, 95% CI) g/person/day, which accounted
for 2.23% of the household solid waste stream. The major waste categories contrib-
uting to total HHW were home cleaning products (21.33%), medicines (17.67%),
and personal care products (15.19%). Packaging and containers (one way) and
products (single use) accounted for over 80% of total HHW generation, implying
a considerable potential to mitigate HHW generation by changing the packaging
design and materials used by manufacturing enterprises.
It has been proven in many scientific researches that workers in solid waste
management (SWM) facilities suffer from several diseases (of major or minor
importance) due to their occupations. Manual sorting may be associated with
exposures to large quantities of airborne bacteria, endotoxin (Poulsen and Dandanell
1995), and in general toxic compounds. The range of those diseases is very wide,
and one of the major sources of uncertainty is that it usually takes several decades for
a person to develop any symptoms of the (potentially severe) illness (Kontogianni
and Karagiannidis 2009). The aforementioned is enhanced by the results of a recent
study conducted in MRFs in the UK, where the scientists pinpointed health symp-
toms in employees which varied in terms of severity and frequency according to the
length of time working and their assignment.
Dental Waste Stream

EU has not yet enacted specific legislation on DW management, which is therefore
covered by a more generic legislation related to medical waste. Dental associations
and/or health ministries of certain EU member states (e.g., the Netherlands, Sweden,
Denmark, France, New Zealand, and Switzerland) have taken measures toward their
sustainable management (WSDA 2004) as the ones indicated below:
• Best management practices (BMP) late on commented implementation.

• DW management guidelines have been handed to dentists by the dental
associations.
• Dental amalgam use banning (as soon as each of their National Boards of Health
is convinced that available non-mercury alternatives have full substitution
capabilities).
• Strict law forcing each dental unit to have a disposal contract with a local disposal
company, and the cost is included in the total cost of each dental therapy.
DW for the last two decades has been a “silent” fraction; its existence among
MSW preoccupied the dentists, their associations, and the Hellenic Ministry of
Health since they were not considered as part of the overall waste resulting from
healthcare activities. Until recently, no measures were undertaken to avoid their
disposal in municipal bins or the health impacts derived from this practice. Only
recently, a new law (Common ministerial decision 1537/2012) introduced DW as
one of the healthcare waste fractions, which need to be separately managed and
treated. Unfortunately, for the time being (16 months after the law enactment), DW is
still disposed along with MSW violating the existing aforementioned law. The
reason is mainly due to the delay of the informational campaign conduction by
those responsible for the overall planning as well as the lack of equipment
procurement by the responsible dentists (e.g., amalgam separators) (Dental Associ-

ation of Thessaloniki).
A pyrolytic incineration facility for medical wastes that could manage certain DW
already exists, but numerous encountered problems (regarding the healthcare waste
collection, transportation and management often-excessive entailed costs as well as
competition from various mobile autoclave units) are aggravating its operation
(Sanida et al. 2004). DW management cost seems to be a particularly important
issue that complicates motivation toward management issues. Thereby, usual every-
day practice still includes dumping the majority of dental solid wastes into house-
hold disposal sites and sanitary landfills without any recycling and separation
process (Kontogianni et al. 2008).
Material and Methods
Determination of the Xenobiotic Compounds
The organization of the overall research was a prerequisite for determining the exact
waste flows of the selected waste fractions as in the case of Greece. The microen-
vironments (mE) and checkpoints where the chemical compounds of both investi-
gated fractions were studied are depicted in Fig. 1.
Both fractions’ waste identity is altered in transition from mE I to II due to factors
such as compression in waste collection vehicles, high temperatures, etc. which lead
to anaerobic conditions where the reactivity among chemicals is high and the
I
Recycling
bins
Material
Recovery
Facility
HHW generation
DW generation Transfer Sanitary

station landfill
Municipal
bins
II
Composting
facility
Fig. 1 Determination of the research microenvironments: (I) bins and material recovery facilities
and (II) transfer stations, sanitary landfills, and composting facilities
outcome cannot be predicted. Due to this fact, research was performed toward the
determination of existing chemicals separately in the two individual mE.
Chemical compounds of the first mE were determined through the conduction of
interviews with producers and sellers of the corresponding products of both inves-
tigated waste fractions. Additionally, contacts were made with international associ-
ations who have performed investigations on those products’ chemical compounds
(e.g., AISE) and international reports. On the other hand, chemical compounds of
the second mE were retrieved from international bibliography and scientific papers
for both fractions: HHW (Gurski 1995; Gendebien et al. 2002; Slack et al. 2005;
Schrab et al. 1993; Karpinski and Glaub 1994) and DW (Miller et al. 1986; Lohbauer
2010; Van Landuyt et al. 2007; Hagiwara et al. 2006).
Overall, for both waste fractions, 125 chemical compounds were listed in the first
mE and 86 for the second mE. The categorization and processing of information for
each one of the listed chemicals assisted in the development of extended databases.
Development of Databases and Linkage to the Population Target

Group
The chemical listing was followed by the determination of their properties based on
information retrieved from EU legislation (OJ 2000, 2008a), international databases
(i.e., IRIS), and scientific papers and reports (Gendebien et al. 2002; EEA 2010;
Turner 1980; Kontogianni 2013; Slack et al. 2005). The categorization was
performed based on the hazard symbol, risk phrases (Rx), and risk combination
(Rx/Ry/Rz/, etc.) of each individual chemical compound. The data processing
presented researchers with preliminary data regarding the hazardousness of the
investigated fractions.
Information regarding each individual chemical compound risk phrase and the
risk combination phrase retrieved from CLP legislation (OJ 2008b) proved valuable
to create a linkage between the existence of those waste fractions among MSW and
the potential impact on SWM facilities’ personnel who were the primal population
target of this research. Toward this, a list of parameters which are endangering health
and safety conditions in any given facility was developed in order for their potential
influence from chemical compound properties to be investigated.
Uncertainty Level Assessment for Both Fractions
Unlike consumer products, the waste does not have a fixed composition even though
it comes from it. Their quantity can be estimated by carrying out a field investigation
and by trying to limit the involved errors, but as far as qualitative recommendation is
concerned, the uncertainty factor comes in anyway and is categorized as follows:
• Qualitative composition of the waste that can be changed during the use of it
before it is transformed into waste (e.g., due to mixing with another product of
same category or due to reactions among its active ingredients)
• Mixing with other categories of waste due to joint rejection, mismanagement, or

non-application of segregation
In the routes that a waste follows starting from production to final disposal,
uncertainty may be significantly reduced or limited, but its description is qualitative.
The calibration of the effects of HHW and DW and the uncertainty estimation
presuppose the definition of the steps of their management. The individual steps
need to be determined and described in terms of properties and dangers in order for
the waste fraction hazards to be assessed.
There are three steps in addressing uncertainties using the statistical approach
(Soltani et al. 2017):
• Finding the origin of uncertainties and estimating them

• Evaluating the impacts of uncertainties on outputs
• Explaining and presenting the results
The description focuses on the two steps and their influence on the overall
composition under the prism of the influence factors. According to the current
situation, the management chain is completed by the final disposal of the wastes in
the sanitary landfill or their treatment in a MRF in order to be forwarded as
secondary raw materials to another production process. The steps are hereby
presented:
• Β1: Temporal storage in the generation site (house/dentistry)

• Β2: Mixing with other materials in the temporal storage bin
• Β3.1: Disposal in municipal bins (mixed waste)
• Β3.2: Disposal in municipal bins (recyclables)
• Β4: Collection and compaction within transportation vehicles
• Β5: Transportation to transfer stations
• Β6: Handling in MRF
• Β7: Final disposal in sanitary landfill
• Ε: Temporal storage in MRF
According to 2008/98/EC (which amended the EU directive 75/442), waste is

“every object, product or compound whose owner disposed or intends or is obliged
to dispose.” The definition includes uncertainty due to the inadequacies in the disposal
route or even the interpretation of these (Hoffmann and Hammonds 1994). In the
case of HHW and DW fractions (given that they are not investigated on a great scale
so there are not many available and cross-referenced data), the estimation of the
disposal impact of the streams is an apprehension of estimation that involves
“uncertainty.”
The objective properties of the MSW stream are assessed based on the techno-
logical and scientific data and questions that have arisen about it (e.g., the level
of risk or harmful effects on the environment). For this reason, three levels of
analysis were developed, backed-up with the corresponding criteria, which are
presented below:
• Uncertainty level (concerning composition, concerning impurities)

• Potential environmental impacts (greenhouse effect, acidification, eutrophication,
ecotoxic properties, toxicity to humans)
• Potential safety risks (fire, biological hazards, reactivity risks)
Health and Safety in Solid Waste Management Facilities
Solid waste management (SWM) facilities in terms of OHS requirements present no

major differences to those existing for all other industrial facilities but often attract
much more political and social attention for obvious reasons pertaining to SWM.
The latter comprises of a wide range of activities encompassing reduction, recycling,
segregation (separation), modification, treatment, incineration, and disposal at vary-
ing levels of sophistication (Hamer 2003). Besides the accidents related with
mechanical and electrical equipment handling, by personnel with no adequate
expertise, undercover hazards related to multitude health problems among workers
at WM plants exist. They are partly owed to the composition of the treated waste
(e.g., handling of organic waste, in landfills, potential existence of medical or other
types of hazardous waste, etc.), the chemical nature of the waste (e.g., toxic,
corrosive, etc.), and the parameters which increase the chemical reactivity. The
health problems in SWM facilities involve pulmonary disorders and gastrointestinal
problems due to high concentrations of total airborne dust, bacteria, fecal coliform
bacteria, and fungal spores. Also the labors suffer from symptoms of organic dust
toxic syndrome (cough, chest tightness, dyspnea, influenza-like symptoms such as
chills, fever, muscle ache, joint pain, fatigue, and headache); gastrointestinal prob-
lems such as nausea and diarrhea; irritation of the skin, eye, and mucous membranes
of the nose and upper airways; etc. (Gladding et al. 2003).
To ensure the validity of the research, the outcomes of the health and safety
research were taken into consideration; based on the outcomes, certain parameters
were taken into consideration and applied where necessary (Kontogianni and
Moussiopoulos 2017). Those are listed below:
• Presence of dust
• Filter maintenance program
• Use of security equipment
• Knowledge of first aid
• The presence of responsible safety officer
• The presence of garbage on the perimeter
• The presence of unwanted animals and birds
• Possibility of fire nearby
The abovementioned parameters calibrated the health and safety status in Hel-
lenic facilities; MRFs, transfer stations, and sanitary landfills (taken into consider-
ation in the present study) are among them. The overall results for all the investigated
SWM facilities in Greece are presented in Table 1.
Table 1 Average calculated hazard level per facility type out of the SWM facilities investigated
(Based on Kontogianni and Moussiopoulos 2017)
Facility type Calculated average hazard level Hazard level clarification
Sanitary landfills 5 Low
Material recovery 5.375 Low
Hazard Assessment
The development of scenarios was based on the what-if methodology and specifi-
cally the potential events that may occur during the processes involved in the
management of MSWs and on the hazard identified because of the presence of
HHW and DW fractions in them.
Through the question-answer process, scenarios are produced, and the answers
lead to the identification of conditions to be dealt with, results and practices that can
mitigate or eliminate the hazard, and potential risks. The disadvantage of the method
is that it relies heavily on the experience of those who apply it, so there is a
possibility that a parameter of the study object is ignored; it was supported by
other tools as well (hazard and operability study (HAZOR), fault tree analysis
(FTA)). Following the process, both scenarios and conclusions emerge.
Due to the structure of the database with the HHW and DW compounds, it was
considered as an optimal and most effective solution to examine separately the
following: the disposal bins (composite or recyclable), MRF, transfer stations, and
sanitary landfills.
The scenarios are designed to investigate the hazard on a case-by-case basis and
have emerged by examining the data of each of the two mE (as presented in
section “Determination of the Xenobiotic Compounds”). There are combinations
that have to do with any given property of HHW or DW chemical compounds as well
as the conditions prevailing in each mE and the potential impacts on SWM facility
labors, citizens, and urban area.
The scenarios that were investigated took into account the following by the
application of appropriate indexes:
• Properties of the included chemical compound in the investigated fractions

• Uncertainty level of each investigated fraction
• Ranking of the health and safety status in corresponding facilities and urban area
Results
Uncertainty Analysis Results
The uncertainty analysis was carried out separately for the two pathways that can be
followed by the HHW stream (management with mixed municipal waste, manage-
ment as recyclables). The management path of DW is considered only one: man-
agement with mixed waste and final disposal in sanitary landfill.
0
B1 B2 B3.1 B3.2 B4 B5 B6 B7 E1
Uncertainty level Potential environmental impacts
Potential safety risks
Fig. 2 Uncertainty level assessment results for the potential management routes that HHW and
DW fractions may follow as components of the MSW stream
The uncertainty calibration was performed on a scale of 0–5 (low and high levels
of uncertainty, respectively) based on a series of chemical compound-related criteria
and the databases as described in section “Determination of the Xenobiotic Com-
pounds”, in addition with the criteria presented in section “Uncertainty Level
Assessment for Both Fractions”.
Figure 2 illustrates the overall uncertainty for HHW and DW streams for all the
individual stages of their management. Both the risk and the uncertainty of the current
content appear to be increasing as their management proceeds and they intensify, as
they do not follow a separate appropriate management course with the appropriate
security measures for the population, the facility labors, and the environment.
With an extensive field research, one can determine the amount of HHW or DW,
and at the same time, in collaboration with the production companies, their chemical
content can be identified; the chemical reactions that are taking place are difficult to
be determined because they depend on factors such as frequency of disposal,
collection frequency, meteorological conditions, etc. The formation of the chemical
compound in each mE took into consideration the results and applied certain
uncertainty factors affecting the probability of chemical compounds’ existence and
their property hazards. Besides, knowing about the most affecting uncertainties can
help the stakeholders adjust their expectations and improve their negotiation out-
comes as Soltani et al. (2017) indicate.
Chemical Compound Properties in Determined Microenvironments
The chemical compounds contained in HHW have a wide range of properties.

Figure 3 presents the outcomes in mE I where those chemical compounds, which
are harmful and hazardous for the environment, constitute the higher percentage.
65%
52%
39%
26%
13%
0%
Flammable Harmful (Xn) Irritating (Xi) Toxic (T) Hazardous Corrosive (C) Oxidising (O) Biological (B)
(F/F+) for the
environment
(N)
Cleaning products Craft and laboratory products Garden care products Average
Fig. 3 Percentage of the properties of the chemical compounds included in hazardous household
waste fraction because of their presence in microenvironment I (municipal and recycling bins and
material recycling facilities)
The latter is due to their existence in garden care products; the results introduce
concerns regarding the use of such products in households and at the same time their
chemical compounds’ distribution in surface and underground waters.
The infectious character of DW, which coexists with the chemical content and the
hazard arising from it, introduced difficulties to the overall investigation of this waste
fraction. Nevertheless, the infectious character was not taken into account since it
has been extensively investigated in the case of medical waste. Twenty-four chem-
ical compounds were listed to be existent in DW fraction, and they constitute the
most common chemical compounds in dental products. It must be noted that
chemical compounds, which are present in illegal medicines or products
unauthorized by the Hellenic Medicines Association, were not taken into account
in the conducted research.
Primal information processing proved that there are compounds with various
properties, and Fig. 4 presents their properties percentage in DW fraction and HHW
fraction in mE II. In this case, where both fractions are present, one can assume that
the chemical compounds’ reactivity is higher because of the anaerobic conditions in
mE I. That is the reason that the properties of the included chemicals appear in lower
percentage than that of the previous case (depicted in Fig. 2).
Health and Safety Condition Influence due to Chemical Compounds

Contained in Investigated Waste Fractions

The processing of data regarding HHW proved that when precaution measures are
not applied, on average 4.00% of those compounds involve a toxic risk and 7.16% of
them involve combination risks for humans working in the facility. When health and
45%
HHW DW Average
30%
15%
0%
Flammable Harmful Irritating Toxic (T) Dangerous Corrosive Ɛxidising Biological
(F/F+) (Xn) (Xi) for the (C) (O) (B)
environment
(N)
Fig. 4 Percentage of the properties of the chemical compounds included in hazardous household
waste and dental waste fractions because of their presence in microenvironment II (transfer stations,
sanitary landfills, and composting facilities)
Table 2 Percentages of the chemical compounds of HHW contributing to health and safety risks as
a result of measures not applied
Health and safety measures not applied in the facility. R-phrases Combinations
Equipment for: (%) (%)
Skin protection 14.39 –
Inhalation protection 9.68 –
Eyes and skin protection 10.37 1.25
Eyes and inhalation protection 1.28 5.00
Skin and inhalation protection 3.16 9.17
Eyes, skin, and inhalation protection 0.96 21.25
safety parameters in SWM facilities (indicated in the given mE) are not applied, risks
for the personnel are increasing as depicted in Table 2. HHW fraction percentile in
MSW is estimated to be less than 10%. So the hazard of the HHW fraction is
minimized due to blending with other wastes as well as due to the pickup efficiency
of MSW.
Nevertheless, six chemical compounds bearing increased hazardous properties
were found to be existent in municipal bins as well as in MRF facilities; one of them
belongs to “garden care products” (dimethoate, 60-51-5) and five of them belong to
“craft and laboratory products” (ethylbenzene, 25036-25-3; aromatic hydrocarbons
C9–C12, 67989-52-0; epoxy resin (molecular weight <700), 25068-38-6; aromatic
hydrocarbons C9–C11, 2530-83-8; naphtha, 8030-30-6). All aforementioned chem-
ical compounds are categorized (based on CLP legislation; OJ 2008) to be R45, that
is, compounds “potentially responsible for carcinogenesis.” Additionally, ten more
chemical compounds are categorized as R39/23/24/25, that is, “Toxic: danger of
very serious irreversible effects through inhalation, in contact with skin and if
swallowed.” Most important was the presence of benzene among the chemical
Table 3 Percentages of the chemical compounds of DW contributing to health and safety risks as a
result of measures not applied
Health and safety measures not applied in the facility. R-phrases Combinations
Equipment for: (%) (%)
Skin protection 19.61 –
Inhalation protection 5.88 –
Eyes and skin protection 9.80 11.76
Eyes and inhalation protection 2.94 5.88
Skin and inhalation protection 12.75 5.88
Eyes, skin, and inhalation protection 8.50 35.29
compounds (which is classified as a certain carcinogenic). Its presence in sanitary

landfills (mE II) together with the aforementioned findings raises concerns primarily
for the health and safety of SWM workers.
Dental Waste in the Municipal Fraction

As far as DWs are concerned when precaution measures are not applied, on average
8.82% of those compounds involve a toxic risk and 11.76% of them involve
combination risks for humans. In SWM facilities of mE II, lack of health and safety
measures was noted; the linkage among properties and risk is depicted in Table 3.
The direct use of dental products on patients is potentially the main reason for
which no certain carcinogenic compounds were located. Worries were raised only
for one compound found in products used for prosthetic dentistry (methyl methac-
rylate). It was found to be categorized as R39/23/24/25 (Toxic: danger of very
serious irreversible effects through inhalation, in contact with skin and if swallowed)
and R23/24/25 (Toxic by inhalation, in contact with skin and if swallowed) at the
same time.
Hazard Assessment of Waste Fractions
The conduction of the hazard assessment for the determination of the potential
hazard imposed the composition of Table 4, through which the level of hazard
was defined.
For each one of the four hazard levels, 392 scenarios were investigated regarding
labors and the environment. The results allocation is presented in Fig. 4; 73.66%
of the scenarios proved that the components that are dangerous for the
environment (N) have medium probability of occurrence. The hazard distribution
is the same for hazard levels 2, 3, and 4 (33–34%). In the case of MRF and for a level
3 hazard, the probability of the involved compounds to be harmless is “often likely”
Table 4 Presentation of the reporting parameters for each scenario

Potential risk Level of reported hazarda
High Significant Average Low Nonexistent
Percentage Characterization (4) (3) (2) (1) (0)
>50% Very probable S S S M A
>1/10 Probable S S S L A
>1/102 Often probable S S M L A
>1/103 Often but probable S M M A A
>1/104 Slightly probable M M L A A
>1/105 Not very probable M L L A A
>1/106 Completely not A A A A A
probable
a
Hazard characterization:
None/negligible (Α) = 0, low (L) = 1, medium (M) = 2, significant (S) = 3
to happen, and the hazard level is significant when labors do not apply or are
ignorant of the first aid measures within the facility (0.45% as depicted in Fig. 5).
In the set of scenarios that were run for all the hazard levels examined, several
levels of impact probability occurred. This, in combination with the results of Fig. 4,
suggests that the possibility of a significant level of risk (4) occurring is negligible. In
general, HHW has a negative impact on the MRF’s workforce, and the risk is
moderate for each level of risk control. This is reinforced by the fact that eventual
risk level 1 cases have a very low chance of occurrence. The most important
outcomes of this assessment are summarized as follows:
• 83% of risk level 1 is very unlikely to occur.

• 64.03%v of risk level 2 has medium probability.
• 79.8% of risk level 3 has medium probability.
• 86.73% of risk level 4 has medium probability.
For the case of transfer stations and sanitary landfills, 927 scenarios were
investigated; the average risk is characterized as medium. The medium probability
of risk is the outcome of 57.61% of the scenarios. On the other hand, significant
probability of level 4 hazard occurs when the parameter of “no protection measure
taken” is taken into consideration. Overall, the probability of a level 4 hazard is low
but certainly higher than the one calculated in the case of MRF; high percentages of
risk occurrence were calculated in the case of medium hazard (M) of levels 2, 3,
and 4, being ~59%, ~78%, and ~69%, respectively.
For the case of HHW disposal in municipal bins, 305 scenarios were investigated.
On average, the risk is low and occurs in 45.74% of the scenarios. Overall, the
scenarios proved that in 50.87% of the cases investigated, the probability of any
level of risk to the citizens is negligible; in 16.03% of the cases, it is low; and in
33.10% of the cases, it is medium mainly due to the parameter of “animal’s access in
bins.” On the other hand, the risk due to chemical compound, which bears biological
hazards (DNA corruption, introduction into the food chain, etc.), is high. Similarly,
for the compounds which are characterized as being hazardous for the environment (N),
100% 0.45%
14.73% 18.75% 18.75% 18.75%
22.32% 25.00%
80% 10.27% 6.25% 6.25% 7.59% 46.88%
37.95%
11.61%
19.53%
60%
37.05%
40% 74.55% 75.00% 75.00% 73.66%
66.07% 37.50%
55.47%
20%
25.00%
15.63%
0%
Flammable Harmful Irritating Toxic (T) Dangerous Corrosive Οxidising Biological
(F/F+) (Xn) (Xi) for the (C) (O) (B)
environment
M L A S (N)
Fig. 5 Probability characterization per hazard level category and property of the chemical com-
pounds in hazardous household waste in MRF
it has 50.91% probability of having medium impacts to city environment and

citizens. Mainly based on the later two compounds’ properties, high percentage of
scenarios where the probability of occurrence is medium for hazard levels 2, 3, and
4 was observed (being ~32%, ~37%, and ~56%, respectively).
Dental Waste Fraction
The development of scenarios for the investigation of DW hazard was affected by

the negligible probability of them being treated in MRF; the scenario was considered
nonachievable, so their existence was considered a fact for transfer stations and
sanitary landfills, and 927 scenarios were developed.
On average, the hazard risk is medium (58.04%). The significant hazard risk
(level 4) for those facilities’ labors occurs when parameters such as “the use of
protective equipment” and the “presence of safety officer” are not applied.
The “presence of litter in the perimeter” increases the introduced toxicity in the
flora of the nearby area. Out of the total scenarios which were run for the determination
of hazard risk in the case of DW presence in sanitary landfills and transfer stations,
28 of them show a significant probability of high hazard risk. This disturbing fact is
attributed mainly to the chemical nature of the waste fraction compounds.
Despite the fact that level 1 hazard risk occurs most often (>80%), they concern
negligible hazards, while the significant level hazards 3 and 4 are assessed to have
medium probability of occurrence (~75%) as depicted in Fig. 6. The higher proba-
bilities for hazard risk are summarized as follows:
• Low probability of level 1 hazard risk (~82%)

• Medium probability of level 3 hazard risk (~78%)
• Medium probability of level 4 hazard risk (~74%), και
• Medium probability of level 2 hazard risk (~52%)
Percentage of hazard risk (%)

100%
80%
60%
40%
20%
0%
A L M S
Level of hazard
LEVEL 1 LEVEL 2 LEVEL 3 LEVEL 4 AVERAGE
Fig. 6 Percentage of hazard risk for every level of hazard risk (the average hazard risk is indicated
as well)
100%
25.00%
32.31%
80% 41.67% 37.50% 40.63% 40.63%
60% 25.00%
24.62%
20.83%
33.33% 31.25% 31.25%
40%
50.00%
20% 41.67% 43.08%
25.00% 28.13% 28.13%
0%
Flammable Harmful Irritating Toxic (T) Dangerous Corrosive
(F/F+) (Xn) (Xi) for the (C)
environment
M L A (N)
Fig. 7 Hazard risk characterization per hazard category and per property of the included chemical
compounds of DW fraction in urban areas
Five hundred sixty-four scenarios were investigated for the case of DW presence
in municipal bins, and the average hazard risk is calculated to be as low as 43.25%.
A significant probability of hazard risk was not found (Fig. 7), while the higher
probabilities were calculated when the parameters “existence of litter nearby” and
“existence of animals in bins” were applied. Those parameters are linked and
common within the urban areas. The medium probability of hazard risk is on average
36%, and the low one is 27.71%. It is important to mention that the average is
exceeded only for the case of chemical compounds with the characteristic of being
hazardous for the environment (N) and rises up to 43%. Similarly, it happens with
those that bear corrosive properties (~50%).
Under the average hazard risk calculation, there are no concerns for the intro-
duced risk by the chemical compounds of the DW fraction. However, the individual
study of their properties may be the starting point for a discussion/consultation to

change the composition of some products. Besides it came up that, in level 4 hazard
risk, the probability is medium in 40 of those compounds and negligible for the rest
of them in case the parameter “potential fire in bin” is applied.
Conclusions
Presented in this research paper was the first phase out of an extended (four phases)
research during which researchers aimed to identify the hazardousness of the two
selected fractions (HHW and DW) which currently in Greece are not managed
separately from the MSW (Kontogianni 2013). Any researcher or stakeholder
aiming to design or implement a holistic waste management system to avoid
treatment of hazardous fractions among the MSW and thus prevent occupational
accidents by developing enhanced (integrated) safety procedures can use these
approaches and outcomes since they have a global relevance. The major outcome
of the overall research would be the development of separate HHW collection and
management programs as in other countries worldwide and the incentive for the
actual organization of DW program for all private, public, and university dental units
since the legislation already exists for more than a year in Greece.
The findings regarding the chemical content of the investigated fractions pre-
sented in this paper present strong arguments toward the need of proper management
and implementation of waste hierarchy at higher levels.
The uncertainty about the environmental and safety hazards due to the presence
of these currents throughout the MSW management course rises as it continues its
course from the bin to the final disposal or treatment. The newly introduced HHW
stream and the unobstructed rejection of OA in mixed bins do not favor the
availability of data on the chemical reactions that take place or the exact composition
of the compounds in each product.
The General Chemical State Laboratory, which is a national agency, should adapt
strict measures toward the investigation and frequent recording of the investigated
commercial products’ chemical content to minimize the hazard primarily arising
from their disposal in municipal waste bins (mE I). The introduction of an environ-
mental certificate for such product producers is the means to do so, but the overall
procedure should be overseen by an independent agency to achieve maximum
efficiency. The aforementioned will assist in minimizing the occupational hazard
in SWM facilities, which is due to end-of-life product mismanagement.
Due to the presence of HHW, MRF workers face a 68.37% chance of having
serious (level 4) health impacts, while 68.8% of workers in transfer stations and
sanitary landfills have a significant impact (level 3). For the first case mentioned, 14
substances and for the second one, 10 substances were tested for their toxicological
effect. Three and four of these substances were considered the most toxic with
certain toxic effects in the body and for which their critical concentration in the air
of the workplace was examined.
It is necessary and urgent that the strengthening of health and safety measures and
intensive training of occupational health and safety officers and personnel in SWM
facilities be a prerequisite to minimize the impacts of the chemicals’ properties

mostly in mE II. Besides the existence of a structured plan for every facility, the
frequent medical examinations (under management supervision and not after per-
sonnel’s initiative and charge) will seriously act toward the prevention of health risks
related to this working activity.
Cross-References
▶ A Review on Treatment of Pharmaceuticals and Personal Care Products (PPCPs)

in Water and Wastewater
▶ Household Hazardous Waste Quantification, Characterization, and Management
in Developing Countries’ Cities: A Case Study
▶ Sustainable Biomedical Waste Management
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Management of Hazardous Paper Mill
Wastes for Sustainable Agriculture 27
A. K. Sannigrahi
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
Raw Materials Used in Indian Paper Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 682
Generation of Wastes in Paper Mill . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683
Quantity and Quality of Paper Mill Solid Wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
Harmful Impact of Paper Mill Wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 686
Reuse of Paper Mill Solid Wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 687
Mass Utilization of Paper Mill Waste Through Low-Cost Composting Technique . . . . . . . . . . . 690
Advantages of Vermicomposting for Sustainable Agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 695
Social Benefits of Vermicomposting of Paper Mill Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 697
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 697
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 698
Abstract
The papermaking has far-reaching environmental impacts due to the production of
wastes in the form of sludge since that is creating major problems to soil, crop, and
human health due to the presence of different toxic chemicals like arsenic, cad-
mium, chromium, lead, mercury, nickel, etc. India has about 700 pulp and paper
mills, which are generally considered as most polluting industries. Different paper
mills use different raw materials like bamboo, wood, paddy straw, waste papers,
etc. The quality of effluents also varies with quality of inputs/raw materials as well
as technical procedures followed in papermaking. Paper mill wastes are the
residuals constituted with fibers produced from the pulping of raw materials but
unsuitable for papermaking, paper sludge, lime sludge, inks, fly ash, clays, and
other fillers developed in de-inking process. These solid wastes in some cases are
A. K. Sannigrahi (*)
Proof & Experimental Establishment (PXE), Defence Research and Development Organization,
Balasore, India

https://doi.org/10.1007/978-3-319-73645-7_17
680 A. K. Sannigrahi
utilized for energy generation, but in many places those are disposed of by
dumping on land by the side of effluent channel. Management of these solid wastes
for beneficial utilization is a great challenge not only to the management authority
of paper industry but also the scientific community for finding out some amicable
solutions. Since this solid waste contains a considerable quantity of organic matter,
this must be utilized for some beneficial purposes. Vermicomposting is the rapid as
well as cost-effective treatment method for recycling the organic solid waste
through the action of earthworms. The worms act as an aerator, a grinder, a crusher,
a chemical degrader, and a biological stimulator. Worms decompose the organic
fraction in the sewage sludge, mineralize the nutrients, ingest the heavy metals, and
devour the pathogens (bacteria, fungi, nematodes, and protozoa). Paper mill wastes
are not easy material to compost and normally need both structural and nitrogen
amendments using different organic matters like sawdust, fruit and vegetable
wastes, food processing industry’s wastes, leaf litters, cow dung, pig wastes,
poultry wastes, water hyacinth, municipal solid wastes, etc. before composting.
Vermicomposting of paper mill wastes is not only a value addition to problematic
wastes but also its beneficial utilization for sustaining organic agriculture. It helps
to reduce the problem of environment pollution and creates an opportunity for
employment generation.
Keywords
Earthworm · Energy recovery · Hazardous waste · Heavy metals · Landfill · Land
spreading · Paper mill wastes · Pulp and paper mill sludge · Social benefits ·
Sustainable agriculture · Vermicomposting · Waste quality
Introduction
The knowledge on paper manufacturing process, though developed in China in

105 AD, spread to other countries through silk and trade routes and reached to India
around 605 AD. The evolution of papermaking and creation of paper products
occurred over centuries, not in overnight. The manufacturing process got momentum
in global arena in 1282 AD with the invention of paper mill. British literature revealed
about the early establishment of different categories of paper mills in India during the
sixteenth to nineteenth century (Ramaseshan 1989). The century-old paper industry
occupies an important position in the Indian economy for its extended role of early
industrialization and social sector development. At present Indian paper industry is
among the top 15 global players with total installed capacity more than 15 million
tons. According to IPMA (2016), this industry has grown from just 17 mills in 1951
with a capacity of 0.14 million tons to 825 mills now with a capacity of 15.3 million
tons. The total installed capacity of the paper industry has grown at a compounded
annual growth rate (CAGR) of 6% over the past decade. The changing policy focus of
Indian government, like economic liberalization in 1991, de-licensing of pulp and
paper sector in 1997, allowing 100% foreign direct investment (FDI), etc., has
changed the growth performance of India’s paper industry, resulting sharp rise in the
27 Management of Hazardous Paper Mill Wastes for Sustainable Agriculture 681
share of India to the world’s total production of paper and paper products from 0.68%
in 1981 to 2.6% in 2016. The number and capacity of industry producing paper in
India during 2001 and 2011 are mentioned in Table 1. Five percent large-scale mills
contribute to 28% of the installed capacity, while medium- and small-scale industries
contribute only 63% and 9% of the total installed capacity (CSE 2013). In 2012,
around 88 paper mills with capacity higher than 50,000 tons per annum (TPA)
contributed to around 60% of the total paper production in India. About 70% of the
total paper production in India is accounted by paper mills situated at Gujarat, West
Bengal, Orissa, Andhra Pradesh, Karnataka, and Maharashtra, while 25% of paper is
produced by mills situated at Uttar Pradesh, Tamil Nadu, Haryana, Kerala, Bihar, and
Assam. The estimated turnover of the industry is approximately INR 50,000 crore
(USD 8 billion), and its contribution to the exchequer is around INR 4500 crore. These
paper industries provide employment to more than 0.5 million people directly and 1.5
million people indirectly (IPMA 2016).
The paper industry is classified into two main segments – paper and paperboard
(comprises of writing, printing, packaging, specialty, and tissue paper) and news-
prints (comprises of newspapers, flyers, and other printed materials intended for
mass distribution). Similar to the production of paper, the domestic consumption of
paper has also been increased from mere 0.83% in 1981 to 2.47% of the world’s total
consumption in 2010. During the last 26 years (1990–2016), domestic consumptions
of newsprint, printing and writing papers, and packaging papers and board have been
increased from 3.95 to 25.4 lakh tons, 9.15 to 46.38 lakh tons, and 9.22 to 75.02 lakh
tons, respectively (Fig. 1). According to the Indian Paper Manufacturers Association
Table 1 Distribution of paper mills in terms of number and capacity

Small scale Medium scale Large scale Average capacity
Year (<10,000 TPA) (10,000–100,000 TPA) (>100,000 TPA) (Tons/annum)
2001 393 (66.1%) 190 (32%) 11 (1.9%) 14,200
2011 314 (45%) 344 (50%) 32 (5%) 22,100
Source: CSE Survey Report (2013)
Printing + writing papers 75.02

News print
Wrapping + Packaging paper + Board
49.4
46.38
41.15
25.4
16.31 18.16 16.52
9.15 9.22 7.5
3.95
1990 2000 2010 2016
Fig. 1 Trend in India’s domestic consumption of paper (Lakh tons) (Source: IPMA survey)
Table 2 Indian paper industry market (production, consumption, export, and import of paper)
(million tons)
Group 2011–2012 2012–2013 2013–2014 2014–2015
Domestic production 10.1 10.5 11.4 12.2
Exports 0.5 0.5 0.5 0.6
Imports 2.1 2.0 2.2 2.3
Domestic consumption 11.7 12.0 13.1 13.9
Source: IPMA
(IPMA), the major factors for India’s robust paper demand are its economic growth,
increasing literacy rate, rapid urbanization, improvement in living standards, quick
change in lifestyles, better-quality consciousness in publication systems (magazines,
multicolor printings, advertising), etc. As estimated by IPMA, the demand for
domestic consumption of paper in India will go up to 20 and 23.5 million tons by
2020 and 2024, respectively.
Table 2 showed that the demand for domestic product is increased from 11.7 to
13.9 million tons within 2011–2012 to 2014–2015, which will further increase to
23.5 million tons by 2024–2025. The per capita consumption of paper has also been
increased from 9.18 kg in 2009–2010 to around 11 kg at present which is still lower
than the present global average of 56 kg and the Asian average of 40 kg. Increase of
per capita paper consumption by 1 kg will increase the demand by about 1.25 million
tons per annum. Since the domestic demand is on the rise, the fate of Indian paper
industry is more promising in the future.
Raw Materials Used in Indian Paper Industry
Indian paper industry utilizes a wide variety of cellulosic raw materials like wood,
bamboo, bagasse, wheat straw, rice straw, jute sticks, grasses, waste papers, etc., and
paper mills can be categorized into three groups on the basis of used raw materials:
wood-/forest-based mills, agriculture residue-based mills, and waste paper-based mills.
Initially woods and bamboos, the conventional raw materials, were used in large
quantities (84% in 1970) for manufacturing of paper. But the share of these forest-
based raw materials to the total raw material consumption declined over the years in
India due to their fast depletion, gradual price hike, and increasing prohibitory regula-
tions (Fig. 2). Agricultural residues like bagasse, wheat and rice straw, jute sticks, and
grasses gained importance, and small- and medium-sized agro-based paper mills were
encouraged by the government for production during the 1980s and 1990s. Use of
agricultural residues instead of forest-based raw materials was not only sustainable for
paper manufacturing but also helped to reduce the stress of paper production consider-
ably on endangered forests. Pulp formation from agricultural residues takes less time to
cook than wood pulps, resulting in the requirement of less energy, water, as well as
chemicals. But the quick decline in share of agricultural residues on paper production
after 2000 might be due to (a) shorter fiber length, fiber width, excessive amount of
primary fines, and low drainability of agricultural residues like bagasse and straw as
100%
7
90% 9
30
80%
47
70%
70
60%
31
50%
40% 84 22
30%
10
20% 39
31
10% 20
0%
1970 2000 2011 2016
Forest based Agri residue based Waste paper based
Fig. 2 Raw material consumption pattern in India (Source: DIPP Annual report 2012 and 2016)
compared to wood fibers (Mathur et al. 2009); (b) own constraints of agricultural residue
like its seasonal availability, high transportation costs, and more investment in pollution
control equipments; and (c) more emphasis on environmental protection by recycling
wastes and latest development of technologies to use waste paper in place of wood-
based raw materials and encouragement from Indian government in the establishment of
a large number of small-sized recycled fiber-based pulp and paper mills for meeting the
rising paper demand of domestic consumers. Pulp and paper industry is the third largest
water-consuming industrial sector in India. Freshwater consumption in waste paper
mills (75–100 m3/ton of paper) is also comparatively lesser than that in wood-based
(125–200 m3/ton of paper) and agro-based paper mills (125–225 m3/ton of paper)
(Chakrabarti 2006). All these factors have helped waste paper in meteoric rise of its
share in utilization in Indian paper industry from mere 7% in 1970 to 70% in 2016 as
compared to other two groups. In terms of present share in total paper production,
approximately 24% are based on wood, 11% on agro-residues, and 65% on recycled
fiber (IPMA 2016). India’s domestic collection of recycled paper is insufficient to meet
the needs, since a considerable quantity of old newspapers are used for various domestic
purposes like wrapping of materials; supply of grocery items in packets; packaging of
foods, fruits, snacks, etc.; and also glassmaking. India imports almost half of its recycled
paper mainly from the USA, Latin America, and Indonesia. India imports nearly
400,000 tons of pulp, 20,000 tons of recycled paper, and about 2500 tons of finished
paper annually (Mathur et al. 2009).
Generation of Wastes in Paper Mill
Generally, the paper industry is considered as a major consumer of natural resources

(forest products, water) and energy (fossil fuels) and a significant contributor of
pollutant discharges in the form of gaseous, liquid, and solid wastes to the environment
(Hossain and Ismail 2015). The paper industry typically generates large quantities of
wastewater which are a collection from five different unit processes like debarking or
raw material preparation, pulping, bleaching, washing of pulps, and papermaking.
Table 3 summarizes the main pollutants produced during those five processes. The
dark brown-colored effluent is heavily loaded with organic compounds depending on
the nature of the raw material, process, and chemicals used, finished product, and extent
of water reused. It has high biochemical oxygen demand (BOD), chemical oxygen
demand (COD), chlorinated compounds as adsorbable organic halides (AOX),
suspended solids mainly fibers, dissolved lignin and its degradation products, hemi-
celluloses, fatty acids, resin acids, tannins, phenols and sulfur compounds, etc. (Ali and
Sreekrishnan 2001). Various chemical additives are used in paper industry either as
“product aids” for improving the product properties or as “process aids” for enhancing
the productivity of paper machine. Majority of the “product aids” do not end up in
effluent (barring dissolution losses), while most of the “process aids” reappear in
effluent (barring retention aids). Overall pollution effects of paper mill effluent are
(a) oxygen depletion in the receiving water body; (b) the presence of undesirable color,
odor, and taste in the water; (c) reduced photosynthesis; (d) formation of blanket of
suspended solids settling at the bottom of the receiving body of water; (e) death of fish;
and (f) toxicity added to the aquatic life due to the formation of mercaptans, penta-
chlorophenol, sodium pentachlorophenate, etc. (Kakahi et al. 2011). More and more
public awareness about the fate of these pollutants and stringent regulations made by
various authorities are forcing the industry to treat effluents to the required compliance
level before discharging into the environment (D’Souza et al. 2006). In many modern
mills, reduced inputs of toxic chemicals and improved wastewater treatment have
resulted in significant reduction of effluent toxicity (Heuval and Ellis 2002) and of
environmental impacts (Sandstrom and Neuman 2003). The treatment of effluent from
paper mill is, however, always mill-specific and complex. Wastewater treatment
methods followed by pulp and paper mills are chemical coagulation, flocculation,
sedimentation, flotation, filtration, and different biological methods like stabilization
pond, trickling filters, activated sludge process, anaerobic digestion, etc.
Table 3 Major pollutants released from paper- and pulp-making process

Process Pollution
stages Wastewater (v) load Effluent contents
Raw Low Low Suspended solids including bark particles, fiber
material pigments, dirt, grit, BOD, and COD
preparation
Pulping Low High Color, bark particles, soluble wood materials,
resin acids, fatty acids, AOX, VOCs, BOD,
COD, and dissolved inorganics
Bleaching High High Dissolved lignin, color, COD, carbohydrate,
inorganic chlorines, AOX, EOX, VOCs,
chlorophenols, and halogenated hydrocarbons
Papermaking Depends on Low Particulate wastes, organic and inorganic
recycling compounds, COD, and BOD
effluents
Source: Hossain and Ismail (2015)
The gaseous emissions from paper mills mainly originate from energy generation
(steam and electricity). The irritating odor caused by lower organic acids and
reduced sulfur compounds like H2S, methylmercaptan, dimethyl sulfide, etc. devel-
oped from effluent treatment plants, from coal storage yard, and from in-plant
process water circulation system creates the air pollution problem in the neighbor-
hood of paper mills. Annoying odors may also be found in paper mills that have less
water circuit closure.
Quantity and Quality of Paper Mill Solid Wastes
In pulp and paper industry, different types of solid wastes and sludges are gener-
ated. The types and amounts of wastes vary greatly among paper mills depending
on the raw materials used, the paper production process followed in the mills, type
and grade of paper produced, and wastewater treatment technologies followed.
These wastes include bark wood residues, screening rejects, different types of
wastewater treatment sludge, lime sludge, de-inking sludge, fly ash from boiler
operations, etc. (Monte et al. 2009; Yadav and Madan 2013; Bajpai 2015). The
rejects consist of sand, bark, portion of raw materials undesirable for papermaking,
impurities like staples, metal from ring binders, plastic and paper constituents as
fillers, sizing agents, and other chemicals. Green liquor sludge or dregs or lime
sludge is inorganic sludge separated from the chemical recovery cycle. De-inking
sludge contains mainly short fibers or fines, coatings, fillers, ink particles, extrac-
tive substances, and de-inking additives. Wastewater treatment sludge is the com-
bination of primary and secondary or biological sludge. Primary sludge, mostly
fines and fillers, is generated in the clarification of process water by air flotation
technique in primary tanks. Secondary sludge is generated in the clarifier of the
biological units of wastewater treatment. The primary sludge can be dewatered
relatively easier, while secondary sludge is very difficult to dewater. Kraft pulp
process produces about 100 kg waste/air dry ton (Adt) of pulp product, while
semichemical and mechanical processes produce about 60 kg waste/Adt (IPPC
2001). CEPI (2006) reported that 11 million tons of waste was generated during the
production of 99.3 million tons of paper in Europe in 2005 indicating 11% waste
generation during paper production. Kay (2002) mentioned about variation of
waste generation quantity with production of different paper grades from recycled
fiber (Table 4). Joyce et al. (1979) reported about the generation of 40–50 kg dry
sludge during the production of 1 ton paper at a paper mill in North America, of
which approximately 70% was primary sludge and 30% was secondary sludge
(Elliot and Mahmood 2005). Generation of de-inking sludge also depends on types
of paper produced in the mill from recycled fiber, 20% in a newsprint mill to 40%
in a tissue mill (Bajpai 2015). Table 5 presents the approximate amount of solid
waste generation at different sources in paper mill. Although the solid waste
generation in paper mill is unavoidable, its quantity can be reduced by adopting
better in-plant control measures, good housekeeping, and creation of general
consciousness at all levels.
Table 4 Waste generated through the production of different paper grades from recycled fiber
Paper grade Solid waste (dry basis, kg/Adt)
Packaging paper 50–100
Newsprint 170–190
Lightweight coated paper/super calendered paper 450–550
Tissue and market pulp 500–600
Source: Kay (2002)
Table 5 Solid waste generation in paper mill

Solid wastes Approximate quantity
Wood- and bamboo-cutting wastes 40% of raw materials
Bark residue 8–15%
Bagasse pith 12–15% of raw materials
Straw dust, knots, fines 6.5%
Cyclean rejects 30–50 kg/ton of paper
Lime sludge 0.45–0.65 ton/ton of paper
Sludge from effluent treatment plant 40–50 kg/ton of paper
Coal fly ash 0.32–0.37 ton/ton of coal burnt
Harmful Impact of Paper Mill Wastes
The papermaking process is complex with the use of many toxic chemicals as both
“product aids” and “process aids” and has far-reaching environmental impacts due to
the production of wastes that are creating major health problems and environmental
degradation. Presence of high organic content not only creates the problem of high
BOD and COD but also creates immobilization of nitrogen in soil due to high C/N
ratio showing deleterious effect on plant growth. Since conventional bleaching using
chlorine and its compound released large amount of carcinogenic dioxins to the
environment, totally chlorine-free bleaching has been started in modern paper mills
where peracetic acid, ozone, hydrogen peroxide, and oxygen are used for avoiding
this chlorine-related problem. Modern paper mills are also applying some new
technologies like “organic solvent pulping” using ethanol, methanol, etc.; “acetic
acid pulping”; “biopulping” using microbial enzymes like xylanases, pectinases,
cellulases, hemicellulases, ligninases, etc.; and “biobleaching” using white rod
fungi, etc. instead of conventional pulping and bleaching process for reducing the
chemical load in wastes. Paper mill wastes contain a considerable quantity of heavy
metals like cadmium, lead, mercury, vanadium, chromium, nickel, copper, zinc, and
arsenic causing a great concern to the environmentalists. Cadmium, lead, and
mercury got most attention due to their relative toxicity. Some of the heavy metals,
especially cadmium, can deposit in the soil and be absorbed by plants. Mercury can
be transformed into methyl mercury in sediments and be accumulated in the food
chain, especially through water. Excessive levels of heavy metals can provoke a
number of health diseases. Excessive amounts of lead and mercury are especially
dangerous with regard to the damage to the nervous system and fatal life. Mercury
exposure at high levels can harm the brain, heart, lungs, and immune system of
people of all ages. Lead can also give cardiovascular diseases and anemia. Excessive
amounts of cadmium can damage the kidney after long-term exposure. Zinc is also a
heavy metal that damages the human body. Luqman et al. (2013) reported the higher
values of various heavy metals in the paper mill effluent. Abdullah et al. (2015)
found that the concentration of heavy metals in the paper mill sludge varied among
different paper mills in Malaysia, but except chromium the concentrations of other
heavy metals like copper, lead, and cadmium were considerably higher than their
availability in agricultural soils of Malaysia. The higher content of copper in paper
mill sludge might be the result of the addition of cyan ink as additives during
papermaking. Tucker and Douglas (2001) also recorded elevated copper levels in
all de-inking sludges due to the selective concentration of copper from the inks into
the sludge on de-inking. The presence of toxic concentration of mercury, cadmium,
and lead was reported by Ahirwar et al. (2015) in the effluent of Orient Paper Mills,
Amlai (Madhya Pradesh, India). Kumar and Chopra (2016) also recorded higher
values of different heavy metals in the effluent of Uttaranchal Pulp & Paper Mill,
Roorkee (Uttarakhand, India), which might be due to the application of various dyes
in the manufacturing of color papers.
Reuse of Paper Mill Solid Wastes
The modern sustainable management of any production process is highly concerned

about reduction in generation of wastes, decreasing its hazardous nature by adopting
clean technologies and effective disposal of its waste. As mentioned above paper
industry is generating enormous quantities of solid waste, over 70% of which is
presently disposed of in landfills (Yadav and Madan 2013). Even today in many
paper mills situated in different parts of the world, solid waste is generally disposed
of in open dumps or poorly designed landfills causing health hazards by groundwater
contamination. The problems associated with its landfilling are the large volumes
involved, the production of considerable quantity of greenhouse gases in landfill,
and the possibility of hazardous substances leaking into the environment (Monte
et al. 2009). Legislation for protection of environment, decreasing landfill space,
rising landfill costs, and increasing public awareness on the negative effects of
disposing organic material to landfill have drawn more attention toward alternative
strategies for disposal of paper mill wastes. Many innovative approaches have been
made for conversion of paper mill solid waste into useful resource material, but due
to very small market demands, those could not become successful in diverting this
waste from landfill disposal. Efforts have been made to use this waste for energy
recovery, for soil quality enhancement through land spreading, for utilization in
brick and cement industry, and for converting that to some beneficial materials like
oil adsorbent material, heat insulation material, landfill capping material, etc.
Energy recovery from paper mill waste (both rejects and different sludges) using
different thermal processes is very common in Europe. Those processes are efficient
incineration at 850 C or more in fluidized bed and circulating fluid bed combustion
chambers for power and steam generation, sophisticated pyrolysis in the absence of
oxygen to produce a mixture of gaseous and liquid fuel, indirect steam gasification
following pulse combustion technology, wet oxidation at temperatures of 150–330 C
and pressure 1–22 MPa for production of carboxylic acids, super critical water
oxidation at 400–600 C for converting wastewater to reusable water and CO2, and
gasification at 1000–1400 C to produce inflammable gas. High moisture (30–50%) in
paper mill sludge is the limiting factor for energy recovery. Dewatering of sludge is
carried out through centrifugation, band filters, filter presses, and screw presses.
Sludge containing a high level of lignin is easier to dewater than other types of sludge.
Monte et al. (2009) described about advantages and disadvantages of above thermal
process for wastes of paper industry (Table 6). Kunzler (2001) showed that secondary
Table 6 Advantages and disadvantages of various thermal processes for energy recovery from
paper mill wastes
Thermal
process Advantages Disadvantages
Incineration Reduction of the amount of residues Incineration process of high moisture
to be landfilled content paper mill wastes can be energy
deficient
Nearly complete elimination of the Air pollution problems (NOX and SO2
organic materials emissions)
Possible applications for the ashes Toxic metals in residue ashes
obtained Source of chlorinated compounds
High cost due to increasing demand on
the flue gas cleaning
Pyrolysis Non-burning process A consistent waste stream such as tires
and plastics is required to produce a
usable fuel product
Production of mixture of gaseous This technology based on the recovery
and liquid fuels and a solid inert of liquid fuel requires low moisture in
residue the sludge (<20%)
Can be sited at most existing plants Low technical maturity for application
Minimization of air, land, and water to paper sludges
pollution
Conversion of all sludge biomass
fractions into useful energy
Volume reduction by as much as
90% and production of sterile carbon
char
Steam Higher heat transfer rate Application to specific wastes
reforming Low NOX emission
Low operating and maintenance
costs
Production inhibition of dioxins and
furans
Vaporization minimization of toxic
metals
(continued)
Table 6 (continued)
Thermal
process Advantages Disadvantages
Wet No air pollution High cost
oxidation Production of high-pressure steam
Super critical Complete destruction of organic Sludges should have high content of
water material dry substances and small particle size
oxidation No NOX and dioxins formation due Traces of acetic acid and nitrous oxide
to low operating temperature may be formed
Recovery and reuse of salts and
fillers precipitated out of super
critical water
Recovery of all heat of reaction as
steam and as hot water
Gasification Higher efficiency of energy recovery Dewatering and drying of sludge
Reduced environmental emissions Not commercially developed for pulp
and paper sludge treatment
Ability to handle most inorganic Complexity of technology
compounds found in sludge
Ash sintering does not impact on Sludge characteristics which limit
reliability gasification efficiency is not fully
Production of an inert solid waste understood
Source: Monte et al. (2009)
sludge of paper mill contained more nutrients than primary sludge, particularly with
regard to nitrogen and phosphorus. De-inking sludge generally contain high concen-
tration of ash (50–60%) resulting from high loading of clays and fillers. Calcium
carbonate level is higher in lime sludge but lower in newsprint sludge. Secondary
sludge contains fewer amounts of heavy metals, while sludge from de-inking and
waste paper mills has relatively high heavy metals. Ribeiroa et al. 2010 suggested
“land surface spreading” of paper mill wastes in forest and agricultural lands as helpful
in soil quality enhancement. Land spreading is, however, considered preferable to
thermal destruction or landfilling. Due to its CaCO3 content, application of lime
sludge on land having acidic soil was considered as one of the preferred disposal
methods for many years in the UK and Northern Europe (Monte et al. 2009). Deka and
Yasmin (2006) suggested using lime sludge (66.5% CaCO3) from a paper mill at
Jagiroad, Assam, as a cheaper alternative source of liming for management of acidic
water in the fish ponds of Assam. Jemison and Williams (2002), though did not notice
the beneficial or detrimental effect of soil surface mulching of paper mill sludge on
growth and yield of potato, recorded soil improvement with greater water retention
capacity. Structural stability due to application of paper de-inking sludge was
increased in clay and loamy soils but decreased in sandy loam soil (Nemati et al.
2000). However, sludge as land spreading material must be used very carefully due to
an unfavorable C/N ratio, high ion exchange capacity, and possible chromium toxicity
(Norris and Titshall 2011). Presence of excessive copper in paper mill de-inking
sludge is also often the limiting factor in land spreading (Tucker 2005). Sometimes
the use of paper mill waste as land spreading material adjacent to residential areas is
found objectionable due to foul odor.
Necessity to conserve traditional building materials (clay, stone, etc.) that are
facing depletion on the one side and reuse of high ash paper mill sludges, on the
other side, have forced researchers to think fresh for their beneficial utilization
together. Cernec et al. (2005) suggested the use of 5–15% paper mill sludge having
high ash as well as high inorganic fraction as raw materials in the brick produc-
tion industry. They observed that the fiber content increased the porosity of bricks,
resulting in the manufacturing of lighter bricks. It also saved fuel in the oven by
decreasing firing time and made the product more resistant against cracking during
the drying and firing stages. Cement industry is using low ash but high organic
content paper mill sludge as efficient alternative fuel in the production of cement.
Raut et al. (2012) reported the use of short length fibers separated from the waste-
water of waste paper recycled paper mill for making lightweight bricks. Adding
organic fibers with cement composites reduces its thermal conductivity, increases
mechanical strength, and yields lighter composites. Rajput et al. (2012) prepared
excellent quality waste-create bricks [porous, thermally stable up to 280 C, and
meeting standard of IS 3495 (Part 1–3): 1992] using varying content of cotton waste
(1–5 wt%), recycle paper mill waste (89–85 wt%), and fixed content of Portland
cement (10 wt%).
Efforts have also been made for the beneficial use of paper mill waste as adsorp-
tion material for removal of heavy metals (Calace et al. 2003; Ahmaruzzaman 2011)
and phenols (Calace et al. 2002). US patent has been granted for its use as oil absorbent
material (Kok 1983), non-clay oil and grease absorbent (Lowe et al. 1988), and
cellulose absorbent (Eifling and Ebbers 2006). Suryan and Ahluwalia (2012) recorded
more than 70% removal of lead, cadmium, nickel, and copper from aqueous solution
containing 100 mg/l of metal concentration by paper mill waste within 15 min at pH
4.5 with 1% biomass concentration (w/v). There is enormous scope to use paper mill
waste after its conversion as eco-friendly and cheap sorbent materials by oil, chemical,
and transport industries. Dried paper mill waste after mixing with fertilizers or
pesticides can be used as fertilizer or pesticide carrier in agriculture for controlled
releasing of active substances in soil (Dongieux 1999). The thermal conductivity
factor of paper mill sludge lower than 0.055 W/m2 K offers an opportunity for its
possible utilization as fiber cement sheet, the heat insulation material. Zule et al.
(2007) reported about the use of paper mill sludge as an efficient impermeable
hydrodynamic barrier for landfill capping material due to its good chemical, hydro-
dynamic, and geotechnical properties.
Mass Utilization of Paper Mill Waste Through Low-Cost

Composting Technique
As discussed above, high carbon-to-nitrogen (C/N) ratio, high biochemical oxygen

demand (BOD), presence of heavy metals in some cases, and foul odor are limiting
factors for land spreading of paper mill waste. Since this waste contains high
quantity of organic matter and some plant nutrients not directly or immediately
available to crops, composting of paper mill waste with the help of microorganism
is probably the lowest-cost disposal technique with minimal carbon loss. Micro-
organisms break the lignin, cellulose, and hemicelluloses parts of waste and
remove phytotoxic effects of raw wastes during decomposition. Composting not
only helps to reduce C/N ratio, mass, volume, and moisture contents but also
produces an odorless stable material with modest levels of nutrients (Tucker 2005).
Composting of paper mill wastes has opened up new market opportunity, espe-
cially for the container-grown market and the amateur gardening markets. Paper
mill waste, being complex in nature as discussed already, is not an easy material for
composting, and it needs both structural and nitrogen amendments for efficient
conversion to compost. Structural amendment is required for increasing porosity
and supply of oxygen to aerobic microbes. Nitrogen amendment is essential for
reducing high C/N ratio and vital for accelerating growth and efficiency of
microbes. Tucker (2005) showed that structural amendment of paper mill sludge
with vegetable wastes alone was not sufficient to reduce high C/N ratio, addition of
7.6 g urea per kg of sludge-vegetable waste mixture could be able to reduce C/N
ratio, and initial temperature rose to above 60 C for 2 days, essential for effective
sanitization and good-quality composting. According to him best composting
requires C/N ratio of substrate as 20–40:1; oxygen concentration >10%;
adequate P, K, and trace minerals; pH 6.5–8; moisture 50–60%; and free air
space of around 30%. C/N ratio lower than 20:1 may create undesirable odors
due to release of ammonia gas, while C/N ratio higher than 40:1 will provide
insufficient nitrogen for optimal growth of microbial populations, thus slowing the
rate of composting. Kunzler (2001) reported that about 300,000 tons of paper mill
wastes were composted by US paper mills in 1999. Thyagarajan et al. (2010)
successfully converted the secondary treatment sludge of a pulp and paper industry
at Karur, Tamil Nadu, into value-added compost in the period of 90 days by aerobic
co-composting with sawdust in the ratio of 3:1 and by mixing with cow dung +
effective microorganisms as inoculums. Champagne and Westman (2012) also
recorded effective composting within 21 days by mixing three parts biosolids of
St Marys Papers Ltd. (Canada) with bulking agents like one part wood chips and
one part sawdust and bringing C/N ratio from 65 to 30 using nitrogen amendments
like ammonium nitrate and chicken manure. Thermophilic conditions sustained for
12 days reaching a maximum temperature of 52 C and final C/N ratio of 21.
Aerobic composting is always preferable as it emits only CO2, while anaerobic
decomposition helps in emission of greenhouse gases like methane and nitrogen
dioxide.
Vermicomposting is a rapid method of composting where complex mechanical
and biochemical transformation of organic waste takes place through the symbiotic
action of both epigeic earthworms and decomposer microorganisms. Earthworm
plays the role of an aerator, a mixer (by mixing calcium with soft organic materials at
esophagus), a grinder (by grinding soft neutralized organic matter in muscular
gizzard), a chemical degrader (by decomposing ground organic particles with the
help of proteases, lipases, amylases, cellulases, and chitinases secreted in the
intestine), and a biological stimulator (by accelerating the population of beneficial

microbes grown in its gut). Singleton et al. (2003) found bacteria species as efficient
decomposer like Pseudomonas, Mucor, Paenibacillus, Azoarcus, Burkholderia,
Spiroplasma, Alcaligenes, and Acidobacterium associated with the intestine and
vermicasts of Lumbricus rubellus earthworms. Similar to other organic wastes,
earthworms decompose the organic fraction of pulp and paper mill wastes, miner-
alize the nutrients, ingest the heavy metals, and devour the pathogens (harmful
bacteria, fungi, nematodes, and protozoa). Earthworms release coelomic fluids
having antibacterial properties and destroy all pathogens in the waste biomass
(Pierre et al. 1982). Cardoso and Remirez (2002) reported a 90% removal of fecal
coliform and 100% removal of helminthes from sewage sludge by earthworms after
vermicomposting. Earthworm species like Eisenia fetida, Eisenia andrei, Eudrilus
eugeniae, Perionyx excavatus, Lumbricus rubellus, etc. are best suited for
vermicomposting of sludge.
Promising results recorded by different researchers on vermicomposting of pulp
and paper mill wastes using various earthworms and structural amendments are
discussed in details below. Idea of vermicomposting of paper mill sludge was started
by an initial experiment of Butt (1993) in which he investigated two species of
earthworms, Lumbricus terrestris L and Octolasion cyaneum, fed on a paper mill
sludge mixed with yeast extract as a nitrogen source and found that earthworm
response to a particular feed was highly species dependent and C/N ratio around
25 was the optimum. Elvira and Dominguez (1995) observed that Eisenia andrei
earthworms suffered weight loss when those were fed with only paper mill sludge
collected from the National Cellulose Company Ltd. in Spain but they grew dra-
matically when raw sludge was supplemented by rabbit manure, sewage sludge, or
pig or hen slurries, indicating the possible impact of improved nutrient balance and
better microbial populations on their growth. In fact raw paper mill sludge is highly
nutrient deficient for sustaining vermiculture, and hence its blending with other
nutrient-rich materials is a prerequisite. During vermicomposting of paper mill
sludge mixed three parts to one with primary sewage sludge using Eisenia andrei
earthworms, Elvira et al. (1996) recorded significant loss of CO2 from substrate,
increase in total nitrogen, lowering of C/N ratio, and mineralization of metals in the
worm-worked product than in the control (composted without worms).
Vermicomposting is a low-temperature process, but pathogen reduction requires
good thermophilic phase with rising of temperatures about >55 C for more than
3 days. Ndegwa and Thompson (2001) found that composting followed by
vermicomposting of sewage sludge blended with paper mulch was a better treatment
option than vermicomposting alone in raising the required temperature of thermo-
philic phase. Sannigrahi and Sannigrahi (2006) also confirmed that two-stage
composting technique, i.e., initial aerobic composting for about a month in open
space followed by vermicomposting under shade, was the best technique for rapid
vermicomposting of different organic wastes using Eisenia fetida. Raising the height
of aerobic composting bed to >1 m and covering materials with black polythene
sheet helped to raise high temperature (>55 C) inside the bed during thermophilic
phase. In an effort to utilize environmental problematic both paper mill waste and
tomato plant debris in vermicompost preparation, Fernandez-Gomez et al. (2013)
found that 2:1 mixture ratio of tomato plant debris and paper mill sludge was the
most suitable feed ratio for optimum growth and reproduction of Eisenia fetida
during vermicomposting process. Yadav and Madan (2013) also prepared good-
quality vermicompost from paper mill sludge of Star Paper Mills, Saharanpur (Uttar
Pradesh, India), after mixing with combined wastes (mixture of agricultural waste,
municipal waste, and poultry waste) in 1:3 ratio and using Eisenia fetida earth-
worms. Total nitrogen, available phosphorus, and total potassium increased, while
percentage of organic carbon decreased with progress of vermicomposting up to
60 days. During investigation on the feasibility of using Perionyx excavatus to
biotransform solid paper mill sludge of Nagaon Paper Mill (Assam) after mixing
with cow dung and food processing waste (breakfast item making waste) in equal
ratio, Sonowal et al. (2013) found that total nitrogen and phosphorus were increased
by 58.7% and 76.1%, respectively, while total organic carbon was decreased by
74.5%. In similar type of another experiment, the same researchers observed that
mixture of solid paper mill sludge with cow dung and food processing waste in
1.0:0.46:0.04 ratio was the best feed combination for vermicomposting by Eudrilus
eugeniae earthworms (Sonowal et al. 2014). Quintern (2014) recommended addition
of nutrient-rich municipal biosolids with pulp mill solids for highly cost-effective
disposal of both wastes through successful vermicomposting. In a 90-day study to
convert mixed liquor-suspended solids (MLSS) collected from Tamil Nadu News-
print and Papers Limited (TNPL) into vermicompost using Eudrilus eugeniae
earthworms, Ponmani et al. (2014) recorded best performance in a mixture of cow
dung, MLSS, and leaf litter (dried and chopped leaves of mango and eucalyptus)
(1:1:2 combination) with respect to higher nutrient contents and better earthworm
growth. In a similar experiment, Natarajan and Gajendran (2014) also prepared
vermicompost successfully by mixing solid sludge of same paper mill with bed
materials (cow dung, pig waste, and water hyacinth) in the ratio of either 50:50 or
25:75 and observed that more addition of paper mill sludge in bedding material
reduced its suitability for earthworm cocoon formation. Quintern et al. (2016)
reported that MyNOKE in New Zealand produced every year about 20,000 tons of
vermicompost by blending 30,000 tons per year dairy waste (co-decanter dewatered
waste activated sludge and dissolved air flotation sludge) from Fonterra milk
processing plants and 50,000 tons/year pulp and paper mill sludge from Oji Fibre
Solutions Paper Mills. The Noke vermicomposting process developed by Quintern
has grown from vermicomposting 2000 tons of sludge in 2008 to 200,000 tons in
2015. During vermicomposting of solid wastes of waste paper-based Emami Paper
Mill at Balasore (Odisha, India) after structural amendment with different organic
materials, Mohapatra et al. (2017a) found that paper mill waste (PMW) alone was
not palatable to Eisenia fetida; many of them either died or moved away from
the tray.
Amendment of PMW with cabbage leaves was also not promising. However, the
amendment of PMW with cow dung and sawdust in 1:0.5:0.5 produced good
quantity vermicompost in comparatively less time with better survival of earth-

worms (Table 7). Vermicompost of this treatment was also recorded comparatively
higher nutrient contents and performed better growth of paddy seedlings.
In another experiment carried out for studying the role of bed preparation
techniques on vermicomposting of waste paper-based Emami Paper Mill waste
amended with cow dung and sawdust, Mohapatra et al. (2017b) observed that
mixing together all substrates and initial turning twice at 7-day interval gave better
performance in relation to vermicompost production (Table 8), growth of Eisenia
fetida earthworms, and growth of paddy seedlings as compared to other bed prep-
aration techniques by placing different substrate layer wise following six different
arrangements during vermicomposting (Fig. 3).
Table 7 Vermicomposting of Emami Paper Mill wastes amended with different substrates
Period of Earthworms at harvesting

Quantity of mixed raw vermicomposting Vermicompost Nos. (big + Total
materials in beds (days) produced (kg) small) weight (g)
2 kg paper mill waste Not completed 0.35 0.10 5+0 4
(PMW)
1.5 kg (PMW) + 0.5 kg 50 0.67 0.05 10 + 30 15
cow dung (CD)
1 kg PMW + 1 kg CD 45 0.48 0.04 20 + 200 45
0.5 kg PMW + 1.5 kg 40 0.57 0.07 15 + 120 40
CD
1.5 kg PMW + 0.5 kg 50 0.33 0.05 8+6 15
cabbage leaves (CL)
1 kg PMW + 1 kg CL 55 0.16 0.04 10 + 0 20
0.5 kg PMW + 1.5 kg 49 0.30 0.01 2 + 10 3
CL
1 kg PMW + 0.5 kg CL 52 0.34 0.14 5 + 80 10
+ 0.5 kg CD
1.5 kg PMW + 0.5 kg 80 0.66 0.16 25 + 10 52
paddy straw (PS)
1 kg PMW + 0.5 kg PS + 75 0.82 0.05 20 + 80 40
0.5 kg CD
1.5 kg PMW + 0.5 kg 50 0.38 0.08 10 + 5 19
water hyacinth (WH)
1 kg PMW + 1 kg WH 47 0.27 0.03 8 + 15 12
0.5 kg PMW + 1.5 kg 45 0.12 0.02 5 + 10 8
WH
1 kg PMW + 0.5 kg WH 40 0.41 0.12 18 + 20 32
+ 0.5 kg CD
1 kg PMW + 1 kg saw 45 1.84 0.08 20 + 100 64
dust (SD)
1 kg PMW + 0.5 kg SD 30 1.15 0.08 25 + 300 78
+ 0.5 kg CD
Source: Mohapatra et al. (2017a)
Table 8 Vermicomposting of Emami Paper Mill wastes under different bed preparation techniques
Pattern of layer of Earthworms
raw material harvested
[PMW (1 kg), SD
(0.5 kg) and CD Period of Nos. Total
Treatment (0.5 kg)] from vermicomposting Vermicompost (big+ weight
no. bottom to top (days) harvested (kg) small) (g)
T1 Mixture of PMW, 40 0.79 0.04 22 + 150 50
CD, and SD
T2 PMW – CD – SD 65 0.26 0.18 15 + 10 22
T3 PMW – SD – CD 70 0.29 0.17 10 + 8 15
T4 CD – PMW – SD 55 0.37 0.15 10 + 20 20
T5 CD – SD – PMW 65 0.19 0.08 7 + 5 8
T6 SD – CD – PMW 70 0.14 0.06 5 + 0 5
T7 SD – PMW – CD 53 0.43 0.14 10 + 15 12
Source: Mohapatra et al. (2017b)
Fig. 3 Glimpses of some bed preparation (Source: Mohapatra et al. (2017b))
Advantages of Vermicomposting for Sustainable Agriculture
Vermicomposting of organic wastes is many times faster than other conventional

composting techniques due to joint action of earthworms and microorganisms
(Sannigrahi and Chakrabortty 2000). The process of composting becomes faster
with time as the earthworms multiply at very rapid rate doubling their population in
every 60–70 days producing new battalions of degrader worms. Different research
results as discussed above have shown that large quantity of good-quality
vermicompost can easily be prepared from never-ending waste materials of paper
mills after its desired structural amendment with nutrient-rich organic wastes with
the help of locally available epigeic earthworms like Eisenia fetida, Eudrilus
eugeniae, or Perionyx excavatus. The harmful impact of the indiscriminate use of
both chemical fertilizers and chemical pesticides to soil, water, crops, and animals,
even the human being, is an open secret now. Every country is gradually adopting
organic farming technique for their agriculture-horticulture cultivation and even in
pasture development. There is a large requirement of manures, compost, and
vermicompost for making organic farming successful. Use of vermicompost is
beneficial to soil, plant, and environment. Vermicompost in soil acts as store house
of nutrients and reduces various losses of vital nutrients. Application of
vermicompost in soil improves different physicochemical properties of soil as well
as nutrient status in soil and releases nutrients to crop roots in a controlled manner.
Vermicomposting being aerobic in nature avoids development of anaerobic
condition and reduces possibilities of production of different greenhouse gases
from different organic wastes, which is the cause of major concern to environmen-
talists for landfills. Vermicomposting also reduces the load of pathogens in environ-
ment as earthworms kill or feed pathogens during vermicomposting of various
organic wastes. Eisenia fetida earthworms can readily bioaccumulate high concen-
trations of metals including heavy metals such as cadmium, mercury, lead, copper,
manganese, calcium, iron, zinc, etc. in their tissues without affecting their physiol-
ogy during vermicomposting, thus beneficial to environment.
Due to the presence of humic substances like humic acids, humates, gibberellins,
auxins, 3-indole acetic acid, and various other substances, vermicompost promotes
plant growth in multiple ways starting with faster germination, increased development
of both lateral and vertical roots, increased area of root hairs, and even higher root
activity (Quintern et al. 2016). Increased root area, root growth depth, and activity help
in increasing nutrient uptake and access to more available soil water during drier
seasons. Several researchers (Arancon et al. 2004; Roy et al. 2010; Lazcano et al.
2011; Joshi et al. 2013) recorded higher crop yield along with higher number of
blossoms and flowers due to vermicompost application. Vermicompost also has the
potential to suppress plant diseases and to control pests such as insects and nematodes
(Edwards and Arancon 2004; Arancon et al. 2005; Edwards et al. 2007)
Sustainable agriculture deals with production of food, fiber, or other plant or
animal products using organic farming technique that protects the environment,
public health, human communities, and animal welfare. It focuses on producing
long-term crops and livestock while preserving the balanced ecological system
within the environment. It helps to maintain soil quality, to reduce soil degradation
and erosion, to increase biodiversity, to save water, and to maintain healthy envi-
ronment. After independence India has achieved self-sufficiency in food production
by increasing its net production from 50.8 million tons in 1950–1951 to 255.36
million tons in 2012–2013. India is also the second most populous country in the
world with an estimated 1.2 billion people. The success of food security depends on
the production and availability of food grains following sustainable agriculture.
Management of paper mill wastes through vermicomposting, therefore, offers a
great scope for sustainable agriculture in India.
Social Benefits of Vermicomposting of Paper Mill Waste
Vermicompost is a marketable product and offers a scope of extra income to

housewives and other family members besides using it in potted plants or in kitchen
garden. Pulp and paper waste solids can be combined with other high nutrient waste
sources, such as municipal biosolids, to increase the nutrient value of the resulting
vermicompost. The vermicomposting work is indeed a value addition to problematic
paper mill wastes but also a great help for beneficial utilization of this by-product for
better crop growth. Vermicomposting is an easy technique and easily understandable
to all people irrespective to their age, gender, educational qualification, or cast. It
creates an opportunity for future employment generation by selling the processed
vermicomposts to organic farmers. Paper mill solid waste can be used as a resource
material for producing good-quality vermicompost essential for better agricultural
growth and for enhancement in soil fertility. This technique shows the path way for
maintaining better health and hygiene of the society.
Conclusion
Paper mill waste, though complex in nature, sometimes contaminated with toxic
heavy metals, and problematic to healthy environment, can be managed following
destructive method of incineration for energy recovery or by constructive method of
vermicomposting for producing quality organic manure essential for sustainable
agriculture. Human health depends on healthy food, non-contaminated water, and
pollution-free environment. Low-cost easy vermicomposting of paper mill wastes
plays an important role in maintaining health of the environment (soil, water, and
air), crops, animals, and human being besides offering enormous scope of employ-
ment generation, provision for side income for family members, and economical
upliftment to the society.
Cross-References

and Prioritizing the Cost-Effective, Eco-friendly, and Sustainable Biotechnologi-
cal Intervention
▶ Biofilm-Based Systems for Industrial Wastewater Treatment
▶ Economic Assessment of Provisioning a Comprehensive Solid Waste Manage-
ment System: A Case Study of Urban Agglomerations in Ganga River Basin
▶ Industrial Solid Waste Management in a Developing Country Governorate and the
Opportunities for the Application of Cleaner Production Principles
▶ Management of Hazardous Paper Mill Wastes for Sustainable Agriculture
▶ Role of Earthworms in Managing Soil Contamination

Constraints
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Management of Municipal Solid Waste in
Morocco: The Size Effect in the Distribution 28
of Combustible Components and
Evaluation of the Fuel Fractions
A. Ouigmane, Otmane Boudouch, Aziz Hasib, and M. Berkani
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 702
Waste Management in Morocco . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 703
General Data on Waste Management in Morocco . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 703
Accompanying Measures in the Waste Sector in Morocco . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 703
Waste Recovery: SRF Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 704
Development of SRF Production in Developed Countries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 704
Recovery Modes of SRF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 705
A. Ouigmane
Laboratory of Spectro-Chemistry Applied and Environment, University Sultan MoulaySlimane,
BeniMellal, Morocco
Laboratory of Environment and Valorization of Agro-Resources, University Sultan
MoulaySlimane, BeniMellal, Morocco
Transdisciplinary Team of Analytical Sciences for Sustainable Development, University Sultan
MoulaySlimane, Beni Mellal, Morocco
e-mail: ouigmaneabdellah@gmail.com
O. Boudouch
Transdisciplinary Team of Analytical Sciences for Sustainable Development, University Sultan
MoulaySlimane, Beni Mellal, Morocco
Environmental and Agro-Industries Processes Team, University Sultan Moulay Slimane,
Beni Mellal, Morocco
e-mail: oboudouch@gmail.com
A. Hasib (*)
Laboratory of Environment and Valorization of Agro-Resources, Sultan Moulay Slimane
University, Beni Mellal, Morocco
e-mail: azhasib@yahoo.fr
M. Berkani
Laboratory of Spectro-Chemistry Applied and Environment, University Sultan MoulaySlimane,
BeniMellal, Morocco
e-mail: m.berkani@gmx.fr

https://doi.org/10.1007/978-3-319-73645-7_82
702 A. Ouigmane et al.
Production of SRF in Developing Countries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 705

Initiation to a Study of the Combustible Fractions Contained in the MSW of the
City of Beni Mellal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 706
Presentation of the Study Area: The City of Beni Mellal, Morocco . . . . . . . . . . . . . . . . . . . . . . . 706
Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 706
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 707
Discussion of Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 710
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 712
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 712
Abstract
The management of Municipal Solid Waste (MSW) is an obstacle in several local
communities, seen the socioeconomic and environmental impacts that may be related
to this sector. Waste generation is usually related to changing demographic figures and
the improvement of living standards. The aim of this study is to search the problems of
waste management in the region of Beni Mellal-Khenifra located in Morocco and to
initiate a feasibility study in order to produce a Solid Recovery Fuel (SRF) from MSW.
The generation of MSW in Morocco is in continuous evolution with an annual
production of 5.3 million tons in urban areas (0.76 kg per capita per day) and 1.47
million tons in rural areas (0.28 Kg per capita per day). The waste management
mode practiced in Morocco is disposal in controlled or noncontrolled landfill.
In order to resolve problems associated with the landfilling impacts, efforts must
be made to look for valorization solutions adopted for the Moroccan context. This
chapter aims to initiate a study on combustible fractions in MSW to encourage
investment in the SRF production which has shown benefits in developed coun-
tries. We have carried out a characterization of Beni Mellal city waste according
to the MODECOM method in order to identify the effect of the particle size
distribution on repartition of fuels fractions in urban waste in Morocco. The
results we found show that the size less than 80 mm contains a lot of fermentable
materials and that the combustible parts have almost the same distribution for size
between 80 and 250 mm and more than 250 mm with abundance of PLDE,
textiles, and baby diapers.
Keywords
Municipal solid waste · Environmental impacts · Landfill · Solid recovery fuels ·
MODECOM · Fuel fractions
Introduction
MSW is heterogeneous residues, which is constantly increasing as a result of

changes in the population and the improvement of living standards. Thus, the
impacts that may be linked to landfilling have promoted nations to look for recovery
solutions. As a result, several recovery methods have replaced landfilling
(composting, methanization, incineration, pyrolysis, gasification, production of
28 Management of Municipal Solid Waste in Morocco: The Size Effect in. . . 703
SRF, etc.). The production of SRF is a sustainable way of managing nonhazardous

waste; it converts fuel fractions into energy. Several studies have been carried out in
this topic in the developed countries (Wavrer et al. 2010; Federec and Compte-R
2015; Rada et al. 2008; Raggazi and Rada 2012). The SRFs are prepared from the
combustible fractions contained in the rejects of mechanical-biological treatment
(MBT) units, commercial waste, and nonhazardous industrial waste (Rada et al.
2008; Raggazi and Rada 2012; Nasrullahet al. 2015). Other by-products such as
waste water treatment plant (WWTP) sludge and tree pruning olives can be added to
SRF to improve calorific value (Tezanou et al. 2005; Lei et al. 2016; Casado et al.
2016). The use of SRF as a substitute for fossil fuels has shown several economic
and environmental benefits (Porteous 2005; Psomopoulos et al. 2009; Abu-Qudais
and AbuQudais 2000; Kara 2012; Chakraborty et al. 2013).
In this regard, we decided to study the possibility of setting up a process for the energy
recovery of the fuel fractions contained in the MSW produced in developing countries.
The first step that we did is studying the effect of waste size on distribution of SRF.
Waste Management in Morocco
General Data on Waste Management in Morocco
Morocco has not escaped from problems of waste management. Several efforts have
been made to improve the quality of waste management sector (collection, sorting,
disposal, etc.). It has tried to reduce the degree of waste management risks by
preparing an integrated strategy to achieve the objectives.
• Techniques (typology and characteristics of waste, collection techniques adapted to

the urban environment, development of landfill and recovery centers, recovery, etc.)
• Socioeconomic aspect (taking into account populations living directly or indi-
rectly from the recovery and recycling of waste, creation of new professions, etc.)
In Morocco, collection of waste in urban areas is estimated to 5.3 million tons per
year. The industry generates more than 1.5 million tons annually, of which 256,000
tones are hazardous waste. The health sector generates 6000 tons of medical waste
per year (Data from the Ministry of the Environment in Morocco).
Morocco has failed to achieve its goal of converting all its uncontrolled dumping
to controlled landfills by 2015. Today, only about 48% of waste is landfilled in
controlled sites. Tangier and Casablanca remain the two main black spots.
Accompanying Measures in the Waste Sector in Morocco
• National Plan of Municipal Waste (PNDM)
Defined in 2008, this plan was aimed in particular at setting up controlled landfills in
100% of the urban communes of Morocco by 2015. The first PNDM action plan
implemented between 2008 and 2012 has fallen considerably. In 2012, Morocco was
so far from its objectives that the Ministries of the Environment and the Interior
decided in all discretion to extend the deadline to 2020.
By 2016, at least three landfills have been completed and are operational in
Meknes, Marrakesh, and Ifrane. They bring the number of operational landfills to
17 at a target of 75, set at 2020. Controlled landfill should therefore be around 48%
today, according to our calculations based on data from the Ministry of Environment
in June 2016.
There are, however, two major black spots in the urban landscape: Casablanca
and Tangier. Tangier produces more than 300,000 tons of household waste per year
and Casablanca 1.2 million tons.
The other objectives of PNDM:
• Achieve a MSW collection rate of 85% in 2015, 90% in 2020, and 100% in 2030:
in 2016, 85.2% of municipal household waste was collected.
• Rehabilitate 100% of old landfills in 2015 (delayed to 2020): by June 2016,
26 dumps were rehabilitated or closed out of a total of 220.
• Achieve a recycling rate of 20% of the waste produced in 2015 (pushed back to 2022):
in 2016, it accounted for 10% mainly thanks to the work of the informal collectors
who intervene in the garbage disposed cities and on the landfills themselves.
– Sorting, Recycling, and Recovery
The management of MSW in Morocco started by improving access and reducing

environmental impacts, while ensuring landfilling in accordance with national and
international standards, and by closing and rehabilitating wild dumps. Despite the
orientation to landfilling mode, recycling remains the best solution for a sustainable
waste management.
Indeed, landfill remains an option whose environmental impacts are often difficult
to control, despite the precautions taken. It consumes spaces, sometimes at the expense
of productive land, and is not without environmental risks (leachate management, risk
of contamination of water resources and soil, greenhouse gas emissions, etc.)
Moreover, with the continuous increase in the number of landfills, the social
acceptance of these controlled storage sites will be increasingly difficult. As a result,
the development of waste sorting and recycling systems is undoubtedly one of the
pillars of sustainable waste management and remains the solution to limit the extent
of landfills. It also helps to reduce the environmental impacts of the sector by
reducing the amount of waste to be disposed of or treated and saving raw materials.
Waste Recovery: SRF Production
Development of SRF Production in Developed Countries
SRF is a fuel derived from nonhazardous waste produced in accordance with the
requirements of the European standards for SRF, specifically in accordance with
EN15359.This standard provides for the classification of SRF according to an
economic criterion (LCV or lower calorific value), a technical criterion (chlorine

content), and an environmental criterion (mercury content). Five levels have been
defined for each of these criteria.
The production of SRF is complementary to material recovery, seeking to pro-
mote waste that cannot be recycled. Their preparation aims to meet requirements
of both energy recovery and the reduction of contaminants during combustion.
The search for energy sources that are more economical than fossil fuels and less
greenhouse gas emitters is observed in energy-intensive industries. Renewable
energies, but also waste, can constitute these new sources of supply.
From nonhazardous waste, and after extraction of the recyclable fraction, the
SRFs are prepared in such a way as to enable efficient energy recovery in heat and/or
electricity, as a substitute for fossil energy. They are storable and have a relatively
high energy potential (measured by the lower calorific value). The content of
pollutants (halogenated, heavy metals,), moisture content, and particle size must
be compatible with energy recovery, smoke treatment, and requirements for ash
elimination. SRF can be divided into two categories:
• SRF with high quality (or cement grade) (LCV > 18 MJ/kg and chlorine content
<0.5%), mainly used in cement plants
• SRF with good quality (LCV between 12 and 18 MJ chlorine <1.5% which will
be destined for boilers dedicated to SRF).
The characteristics of the SRF depend on the incoming waste and the process of
preparation for their recovery. In practice, the SRF user verifies compliance with its
requirements (technique, environmental, and economic).
Recovery Modes of SRF
In Germany, many thermal power plants use SRF. In France, use is limited to cement
plants, but the cement industry is highly energy intensive (Federec and Compte-R
2015). In order to limit the energy cost of clinker production, studies were carried out
to research an alternative source of energy supply. Also, SRF can be used in
dedicated boilers to replace fossil fuel boilers. In order to optimize the corresponding
investments, these units must operate continuously. They will preferably supply
industries or urban heat networks. Similarly, attention should be paid to the revers-
ibility of the fuels used so as not to hamper the development of material recycling.
SRF could also be recovered in pyrolysis or gasification units, which convert this
solid waste into combustible liquids or gases.
Production of SRF in Developing Countries
There is no study about SRF production in developing countries. It is within the

framework of this study that we will initiate a possibility of development of the
production of SRF in developing countries as Morocco.
Initiation to a Study of the Combustible Fractions Contained

in the MSW of the City of Beni Mellal
Presentation of the Study Area: The City of Beni Mellal, Morocco
The city of Beni Mellal is part of the Beni Mellal-Khénifra region according to the new
regional division admitted to Morocco in 2015, and it extends over a territory of 39 km2
and counted approximately 192,676 inhabitants in 2014 according to general popula-
tion census 2014. It is located in the center of Morocco at the edge of the mountains of
the High Atlas. The city is characterized by a continental climate: cold in winter with
hot summers and an average temperature of 18 C, the following figure shows the
geographical location of the city of Beni Mellal that is the subject of this study (Fig. 1).
The mode of characterization of waste that we use is MODECOM method. Firstly,

we divided the city of Beni Mellal into nine sectors. Over a period of six successive
days we have characterized 10% of the waste collected by each sector.Towards the
end of the day we arrive at characterized 10% of the total flow of MSW produced.
Once the waste is unloaded, they are mixed and quartered. The following step is
transferring a sample from each sector to another platform to undergo a three-part
particle size classification using particle size tables (Fraction 1 (F1): less than
80 mm, Fraction 2 (F2): between 80 and 250 mm, and Fraction 3 (F3): more than
Fig. 1 Localization of study area

250 mm). After finishing the particle size, we have weighed each fraction, and we
have eliminated fraction F1 because it contains the organic matter. Our study aims to
study the behavior of the combustible fraction in MSW (paper, cardboard, textile,
plastics, hygienic waste, wood, shoes and elastomers and various fuels).
Results
Particle Size Separation Result

The granulometric separation of waste plays an important role in their treatment.
After dividing a granulometric separation into three fractions we were able to find
the results which are shown in the table and the following graph (Table 1) (Fig. 2).
Table 1 Results of Average
particle size separation of
tonnage Average mass
6 days/ of sample in
Granulometry sector 7 days Percentage
mm Sector Kg Kg %
F1 less than S1 337.78 2427.80 35.62
80 mm S2 199.07
S3 120.59
S4 147.58
S5 594.6
S6 186.56
S7 376.73
S8 210.9
S9 253.99
F2 between S1 384.24 2932.95 43.03
80 and S2 240.93
250 mm S3 42.28
S4 369.04
S5 234.07
S6 515.85
S7 204.36
S8 511.52
S9 430.66
F3 more than S1 221.96 1454.76 21.34
250 mm S2 184.63
S3 41.65
S4 200.91
S5 163.41
S6 133.1
S7 76.7
S8 215.83
S9 216.57
Total of samples kg/day 6815.49 100
Fig. 2 Distribution of waste

as a function of particle size 21.34 % 35.62 %
43.03 %
F1 less than 80 mm
F2 between 80 and 250 mm
F3 more than 250 mm
Fig. 3 Percentage of fuel

fractions in F2 and F3 100
80
57.79 59.86
60
40
42.21 40.14
20
0
F2 F3
Other waste Fuel fraction
We note that F2 is the most abundant, whereas F1 constitutes only 21.34% of the
waste stream.
Sorting Results of Fuels Fractions

Fraction F1 has not been sorted due to its important composition of fermentable
matter which is not the subject of the present study. On the other hand, the sorting of
fractions F2 and F3 is shown in the following graph (Fig. 3).
The results showed the absence of a large difference between the percentages of
fuel portion for both fractions.
If all waste streams with a size more than 80 mm are taken into account, the fuels
fraction will constitute 41.18% of the total stream as shown in the graph of the
following figure (Fig. 4).
Sorting Results of First Group

The first group is made up of all types of plastics that we can find in MSW. For our
case, we found six types of plastic. Distribution results for this category are shown in
the following graph (Fig. 5).
Fig. 4 Percentage of fuel

fractions for a stream of waste
more than 80 mm
41.18
58.83
Fuels fraction Other wastes

PS
F2
F3
PVC LDPE PP HDPE PET
0 10 20 30 40 50 60
Fig. 5 Distribution results of the first group of fuel fractions
LDPE is the type that we found abundantly in plastics for both fractions F2
and F3.
Sorting Results of the Second Group

This group consists of paper, cardboard, tetra-pack, and hygienic waste. These waste
fractions are considered to be significant calorie resources and can be an important
component in an SRF composition. In addition, the high temperature can destroy the
germs that we can find in hygienic waste especially in baby diapers. The following
graph shows the distribution results of this group as a function of the particle size
distribution (Fig. 6).
Baby diapers are the most abundant in this group and come after other types of
waste.
Sorting Results for the Third Group

The components of this group are textiles, shoes and elastomers, wood, and various
fuels. The distribution results for this group are shown in the following graph
(Fig. 7).
elastomers pak
Shoes and Tetra cardboard Paper and
F2
F3
cardboard
%
0 5 10 15 20 25 30
Fig. 6 Distribution results of the second group of fuel fractions

Various Shoes and Textiles Wood
fuel elastomers
F2
F3
0 5 10 15 20 25
Fig. 7 Distribution results of the third group of fuel fractions
Composition of the Fuel Fraction with a Particle Size More than 80 mm

The results of the composition of the fuel fraction are shown in the following graph
(Fig. 8).
The composition of the fuel component in the city of Beni Mellal shows that
PLDE is the most abundant type of waste and represents 31% of the fuel fractions
followed by sanitary waste 18% and textiles 12%. On the other hand, the percentages
of PVC and PS are low and respectively they constitute 0.3 and 1% of fuels fractions
stream.
Discussion of Results
The results show that MSW of Beni Mellal contain in important quantities of fuel
fractions for a size of waste more than 80 mm. Fraction F1 can influence the quality
Paper and
Shoes / Cardboard
Elastomers 7%
PVC 3%
1% Various fuel Paper Tetra pak
10% 6% 4%
Wood Textiles
2% 12%
Sanitary waste
PS 18%
0%
PLDE
31%
PET
3%
PHDE
PP 1%
2%
Fig. 8 Results of evaluation of fuel fractions in MSW with size more than 80 mm
of the SRF because it contains a lot of organic matter. For this reason, a sieve of
80 mm should be installed to eliminate this fraction which can influence the quality
of SRF. In addition, the removal of F1 contributes to the reduction of the moisture
content in the waste caused by the high rate of fermentable matter in waste generated
in developing countries.
The sorting results for F2 and F3 have shown that the distribution of the
combustible fraction in the waste is the same, which will make it possible to
take into consideration a single granulometry grid to separate the fraction F1 from
the fractions F2 and F3; the mixture of F2 and F3 will have no influence on the
distribution of the combustible fractions. Even the results of the fractions by
group show the absence of the effect of the particle size on the distribution of the
waste except diapers are often produced in comparison to adult diapers, which are
larger in size but have less production, also the size distribution of textiles differ
in F2 and F3 because the source of textiles waste is variable (trousers, socks,
piece of textiles from tailor workshop, etc.,). The following table shows a
comparison of the fuel fractions that we found in our study with others in
developing countries (Table 2).
The comparison of these studies shows that plastic is still the most abundant fuel,
and this value is quite high in Ghana, Nouakchott, and Lome. However, there are
significant quantities of textiles for the Maghreb countries in Algeria and in the
present study.
Table 2 Comparison of fuel fractions of the present study with other studies in developing
countries
Fuels fractions
Paper and Various
Granulometry Plastic cardboard Textiles fuels
Country Author mm % % % %
Beni Present study >80 mm 37.60 16.28 34.43 11.71
Mellal
Nouakchott (Aloueimine 2006) >100 mm 46.92 25.77 25 2.07
Ghana (Kodwo et al. All flow 63.16 22 9 6
2015)
Naama (Youb et al. 2014) >100 mm 20 25.07 53.83 1.32
(Algeria)
Lome (Koledzi 2011) >100 mm 46.5 17.13 21 15.38
Conclusion
This study allows us to draw some conclusions in terms of MSW management in

Morocco, which have an impact on human health and the environment given the
management methods adopted by the municipalities. In this context, two scenarios can
be developed; the first concerns the sorting of waste at the source in two fractions: fuel
and nonfuel fraction. The nonfuel fraction will easily extract the biodegradable material
and treat it biologically and the fuel part will be chained to an SRF production unit. The
second scenario is to set up a grain size grid upstream of the mechanical-biological
treatment units to sort the fraction with size more than 80 mm in part combustible and
noncombustible. The second one will be chained to SRF unit production.
The preparation of SRF does not require sorting of several fractions as other
recoveries modes. It can be a sustainable solution for waste management in devel-
oping countries by reducing the stream of waste sent to landfills.
Cross-References
▶ Hazardous Waste Management with Special Reference to Biological Treatment

▶ Household Hazardous Waste Quantification, Characterization, and Management
in Developing Countries’ Cities: A Case Study
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Hazardous Waste Management with Special
Reference to Biological Treatment 29
Soumya Nair and Jayanthi Abraham
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 716
Characteristic Features of Hazardous Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717
Classes of Hazardous Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717
Treatment of Hazardous Wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717
Physical Treatment Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 718
Thermal Treatment of Hazardous Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 719
Chemical Treatment Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 719
Biological Treatment Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 720
Limitations of Treating Hazardous Wastes Using the Biological Treatment Method . . . . . . . . . 737
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
Abstract
Hazardous waste refers to any unwanted waste or refuse which may be solid or
liquid in nature and is considered lethal, chemically unstable, reactive, combus-
tible, or corrosive, posing a threat to the environment. The most commonly found
hazardous waste in the household includes batteries, pesticides, dry cleaning
agents, metal particles, organic solvents, lubricating oil, etc. Maximum hazardous
wastes are produced by nuclear weapon and power plants. These wastes are toxic
to human health when exposed via contact, breathing, or ingestion. Household
hazardous wastes are less controlled than the industrial hazardous wastes as they
are likely to be discarded inappropriately posing a negative impact to human
health, a threat to the biodiversity and ecosystem at a large scale. These hazardous
wastes may be treated chemically, physically, thermally, or biologically. The
present chapter focusses on the cost-effective and eco-friendly microbial
S. Nair · J. Abraham (*)

Microbial Biotechnology Laboratory, School of Biosciences and Technology, VIT University,
Vellore, Tamil Nadu, India
e-mail: soumyanair37@gmail.com; jayanthi.abraham@gmail.com

https://doi.org/10.1007/978-3-319-73645-7_121
716 S. Nair and J. Abraham
treatment processes involved in hazardous waste management, both unaided and

in combination with the existing treatment methods. The primary goal is to
convert hazardous wastes to its nonhazardous counterpart so that it does not
pose a danger when released in the environment, even better if it can be reused or
recycled. With suitable microorganisms and under optimum environmental
parameters, hazardous bio-refractory wastes can also be degraded. Furthermore,
genetic engineered microorganisms could be a revolution in the microbial treat-
ment of hazardous wastes.
Keywords
Hazardous waste management · Bio-refractory · Microbial treatment ·
Environment · Industrial hazardous wastes · Genetic engineered
microorganisms · Household hazardous wastes
Introduction
Hazardous waste management (HWM) is a major challenge in all the metropolitan

areas of the world. Without an adequate and economical waste management program,
the waste generated from various industries, or due to anthropological activities, can
lead to health jeopardy and have a negative impact on the ecosystem (ADB 2016).
Uncontrolled and continuous discharge of industrial, agricultural, and civic wastes
into the surrounding environmental sink has become a major global concern to be
taken care of (Ash and Fetter 2004; Bullard et al. 2008; Chakraborty and Green 2014).
The industrial and civic activities had also led to the contamination of the agricultural
lands, which results in the loss of biodiversity. Although the use of pesticides and
herbicides increases the productivity of crop, they also increase the contamination of
the soil, water, and air (Gokhale-Welch 2009; Gilbert and Chakraborty 2011; Downey
and Crowder 2011; Das 2015; Dixit and Srivastava 2015).
Hazardous wastes can be categorized as solids, liquids, or gases. For example,
paints, batteries, pesticides, polychlorinated biphenyls (PCBs), solvents, motor oil,
radioactive gas, mercury, etc.
As mentioned earlier, hazardous waste management is a global issue. Each year,
technologically advanced nations with stringent environmental laws and regulations
export more than three million tons of hazardous waste for disposal in poorer or
developing nations with less stringent waste disposal laws, making these lands
polluted (Haq and Chakrabarti 2000, 2007; Kathuria and Haripriya 2000; Kathuria
and Khan 2007; Kathuria 2009; Kohli and Menon 2015).
Hazardous wastes are known to cause serious issues for years after their improper
disposal. Most of the current existing industrialized waste disposal sites were set up,
dumped, and concealed long before establishing the present day standards for the
waste management, which includes the collection, transport, processing, and finally
the disposal of the hazardous wastes. At times, the dumping sites are themselves very
difficult to locate (Ravi 2014; Taylor 2014; Sabapathy et al. 2015). These wastes that
29 Hazardous Waste Management with Special Reference to Biological Treatment 717
are toxic, highly flammable, or corrosive in nature are often persistent in the
environment for a longer period of time. At times, the different risks of their
improper disposal are unknown, but eventually poses a serious threat to its sur-
roundings and indirectly to the human well-being (Ash and Fetter 2004; Anyamani
2009). The industries that are answerable for many of such hazardous waste sites
prior to 1960 are no longer in business and are shut down (Planning Commission
2007; Planning Commission 2012). The current government legislation gives indus-
tries fairly a broad flexibility to synthesize chemicals, monitor and regulate their own
waste disposal practices, and even to challenge cases of possible environmental or
damage to human health. It is often tremendously difficult to prove a scientific link
between an incident of drinking water poisoning, or a human disease cluster, and a
facility that improperly handles industrial chemicals.
Characteristic Features of Hazardous Waste
Hazardous wastes can be identified using a set of characteristic features. They can be
classified on the basis of their nature of the waste as a whole: biological, chemical,
and physical properties. These properties generate one or more of the factors below
on reaction with self or other substances (Carter-Whitney 2007; Balkwaste 2010;
Bernstad et al. 2011).
Classes of Hazardous Waste
There are nine classes of hazardous waste as illustrated in Table 1. Some of the
classes are further subdivided (EPA 2008; Lambeth 2012).
Treatment of Hazardous Wastes
Hazardous waste treatment can be categorized in a number of ways. Categorization

could relate to the treatment method:
(I) Physical
(II) Thermal
(III) Chemical
(IV) Biological
Often waste is subjected to a combination of these methods for effective and safe
disposal. Treating hazardous waste can be complex and expensive. For certain
common hazardous substances, best practice treatment has already been well
established through research and practical experience. For such substances, treat-
ment options are generally easily determined and applied. However, for a number of
more uncommon or problematic wastes and/or mixtures of contaminants, specialist,
Table 1 The different classes of hazardous waste

UN Class
number (1989) Characteristics Types Examples
1 Explosives Projection, Ammonium perchlorate,
Mass explosion, Cyclonite dinitrophenol,
Minor hazard Hexanitrodiphenylamine,
Explosive articles
2 Gases Poisonous, Compressed oxygen,
Flammable gas, Aerosols,
Nonflammable gas Butane,
Ammonia
3 Flammable liquids Low flash point range, Acetone,
Medium flash range, Alcohol,
High flash range Ethyl ether
4 Flammable solids Flammable solids, White phosphorus,
Spontaneous combust, Yellow phosphorus,
Emitting flammable Alkali metals
gases when wet
5 Oxidizing Oxidizing compounds Sodium peroxide,
substances of all types Potassium permanganate,
Potassium super oxide
6 Toxic and infectious Poisonous agents, Arsenic,
substances Infectious agents Clinical waste
7 Radioactive Radioactive Uranium
material compounds of all kinds
8 Corrosives Corrosive in nature Mineral acids,
Organic acids,
Strong bases
9 Toxic Toxic to the ecosystem Environmentally
or society hazardous chemicals
experts may need to identify or develop an appropriate treatment option/process.

Some contaminants may be so complex and/or difficult to treat that the best option
remains to safely store the waste until shipment to an appropriate treatment facility.
Safe storage and transportation in itself may be complex and specialized.
Physical Treatment Techniques
Different physical treatments techniques have been deployed for treating the haz-
ardous wastes. A waste is subjected to physical methods or processes so as to contain
the hazard, to immobilize the hazardous component(s) or substance(s), and/or to
prepare it for further treatment, recycling, or landfill. Physical treatment methods do
not destroy the wastes altogether, instead there are conformational changes that are
easier for further treatment or disposal. Conventional physical treatment methods
include carbon adsorption, filtration, flocculation, distillation, reverse osmosis, and
ion exchange (Lagrega et al. 2001; Sheth and Pandya 2001). Other physical treat-
ment techniques include electro-dialysis, solvent extraction, separation by filtration,
chemical precipitation, solidification and stabilization, chemical fixation, encapsu-
lation, wetting, and ozonation to name a few.
Thermal Treatment of Hazardous Waste
Thermal treatment methods are used at relatively high temperatures

(415 C–1650 C) to break down the organic chemicals present in the hazardous
waste into more simple, less toxic forms in systems with oxygen (incineration) or
without oxygen (pyrolysis).
Wastes are typically combusted in two stages during pyrolysis. The first stage
occurs in the main chamber. The next stage occurs in the secondary chamber, where
gases formed in the main chamber are burned at 976 C–1648 C. In theory, this
second chamber burns off carbon monoxide and organic vapors generated in the first
chamber and avoids vaporization of inorganic material. Inorganic compounds,
which include heavy metals, form an insoluble residue, and those not destroyed by
incineration are to be disposed.
Some of the thermal treatment processes of hazardous wastes are as follows:
thermal desorption, incineration, vitrification, wet and supercritical oxidation,
plasma arc A, rotary kilns, cement kilns, and boilers.
Chemical Treatment Methods
Chemical treatment of hazardous wastes helps us to convert highly toxic and lethal
wastes to its lesser hazardous state or render it nontoxic altogether. This mode of
treatment also helps in recovering beneficial and valuable by-products post the
treatment process of the hazardous wastes. Hence, in this way the overall costs of
waste disposal reduces tremendously. Usually, in most cases, the chemical treatment
method is employed before disposing these hazardous wastes into landfills, so that
the degree of contamination or pollution is reduced to an extent. During a chemical
treatment process, a chemical transformation of the various waste components is
brought about causing either the removal of the lethal component or in the oxidation/
reduction of the particular component of the waste. As mentioned earlier, oxidation
and reduction is two of the examples of a chemical treatment process. The combi-
nation of both physical and chemical treatment helps in concentrating the effluent
first followed by removal of the toxicity before it is dumped into the landfills.
A number of chemical treatment methods are adopted in managing the hazardous
wastes from a number of industries such as tannery, iron and steel, etc. Some of the
many chemical processes are as follows: neutralization, sedimentation, pressure
filtration, hydrolysis, ozonolysis, precipitation, coagulation, and ion exchange to
name a few.
The selection of a particular treatment process among the others depends solely
upon the nature of the waste and the final outcome of the effluent from the waste
stream.
Biological Treatment Methods
Conventional biological treatment methods have been used for over a decade in
industrial waste treatment and hazardous waste treatment plants. Current progress in
the understanding of the existing biological processes has led the researchers to the
development of new biological tools, enhancing the opportunities for bioscience
applications in many areas, including the treatment of hazardous waste. The impact
of these advancements on waste treatment techniques along with the process mod-
ifications and end-product substitutes are an important factor governing the entire
treatment process using biological treatment methods. Biotechnology in some way
or another has a direct role to play in the waste treatment plants. It is a means by
which the researchers can degrade or detoxify the hazardous chemicals present in the
waste effluents.
Aims of using the biological treatment method over the other conventional
methods are as follows:
1. Study of degradation of recalcitrant compounds

2. Measure of the tolerance of severe or frequently changing operating parameters
3. Study of multicompound degradation
4. Study of rates of degradation of heavy metals from the effluents
5. Ability to concentrate the nondegradable compounds and using biological
methods to detoxify the hazardous wastes
Recalcitrant such as benzene, halogenated compounds, and toluene have been

reported to get degraded by certain isolated strains of bacteria and fungus. These
organisms have been further taken forward for strain improvement and genetic
manipulations. It was observed that post strain improvement, these organisms
could degrade the compounds at a faster rate and more efficiently. These strains
can also be used in different remedial situations, such as clean-up of oil spills,
precipitating, and degrading heavy metals from the hazardous wastes. The improve-
ment of the various conventional biological systems through the development and
improvement of specific microbial strains capable of degrading multiple compounds
at a given time has been proposed (Contreras-Ramosa et al. 2008).
However, this approach has also many drawbacks: engineering difficulties,
development of a consortium of organisms working together, etc. Development of
biological pretreatment systems for waste streams has some potential for those
wastes that contain one or two recalcitrant compounds. A pretreatment system
designed to remove a specific toxic compound could reduce the shock effects on a
conventional treatment process. In some cases, a pretreatment system may be used
with other nonbiological treatment methods (i.e., incineration) to remove toxic
compounds that may not be handled in the primary treatment system or to make them
more readily treated by the primary system. In other cases, pretreatment might render
a waste nonhazardous altogether. One area of research in advanced plant genetics is
in the use of plants to accumulate metals and toxic compounds from contaminated
soils.
Current research is directed to four areas. The first area involves the use of plants
to decrease the metal content of contaminated soils, through increased rates of metal
uptake. Plants could be used to remove metals from the soil which gets accumulated
in the plant fibre which can be disposed. The second area of development focuses on
direct metal uptake in nonedible portions of the plant. For example, the development
of a grain crop like wheat that could accumulate metal from soil in the nondurable
parts of the plant would allow commercial use of contaminated land. A third area of
research is directed toward development of crops that can tolerate the presence of
metal without incorporating these toxic elements in plant tissue. Finally, research is
being conducted concerning the use of plants in a manner similar to microorganisms
to degrade high concentrations of hazardous constituents.
Changes in process design incorporating advances in biological treatment sys-
tems may result in less hazardous waste. The development of organisms capable of
degrading specific recalcitrant materials may encourage source separation, treat-
ment, and recycling of process streams that are now mixed with other waste streams
and disposed. The replacement of chemical synthesis processes with biological
processes may result in the reduction of hazardous waste. Two methods of increasing
the rate of chemical reactions are through higher temperatures and catalysts. One
type of catalyst is biological products (enzymes) that inherently require milder, less
toxic conditions than do other catalytic materials. Historically, many biological
processes (fermentations) have been replaced by chemical synthesis. Genetic engi-
neering offers opportunities to improve biological process through reduced side
reactions, higher product concentrations, and more direct routes; thus, genetic
engineering offers a means of partially reversing this trend. The development of
new process approaches would require new reactor designs to take advantage of
higher biological reaction rates and concentrations. Biotechnology also could lead to
substitution of a less or nonhazardous material for a hazardous material, particularly
in the agricultural field. One of the primary thrusts of plant genetics is the develop-
ment of disease-resistant plants, thus reducing the need for commercial products
such as fungicides. Genetic engineering to introduce nitrogen-fixation capabilities
within plants could reduce the use of chemical fertilizers and potentially reduce
hazardous waste generated in the manufacture of those chemicals (Wang and Chen
2006).
Some methods employed in the treatment of hazardous wastes are as follows:
Activated Sludge
An activated sludge treatment process refers to a multichamber bioreactor unit that
makes use of extremely concentrated microorganisms in order to degrade the organic
material present in the wastes and remove nutrients from it and produce a superior
quality effluent. A continuous and well supply of oxygen to the treatment system is
Waste Preliminary Primary Aeration Secondary Final

Disinfection
inflluent treatment clarifier tank clarifier effluent
Primary Sludge Waste activated sludge
Sludge treatment and disposal
Fig. 1 Flowchart of activated sludge treatment process
required to maintain the aerobic conditions running well and to keep the activated
sludge suspended.The activated sludge consists of different flocs of bacteria, pro-
tozoans, algae, and fungi which are suspended and mixed with the waste influent in
an aerated tank. The bacteria utilize the organic pollutants to grow and develop.
At the end, the biomass is converted to energy, water, carbon dioxide, and new cell
material. Flowchart of activated sludge treatment process is shown in Fig. 1.
Microbes and Their Role in Activated Sludge

There are five major groups of microorganisms generally found in the aeration basin
of the activated sludge process. Some of the microorganisms with their active role in
active sludge are listed in Table 2.
1. Bacteria
• They are mainly responsible for the removal of organic nutrients from the
waste water.
• Aerobic bacteria are most commonly found in an activated sludge.
2. Protozoa
• Their primary function is to remove and digest the bacteria and other organ-
isms that are dispersed and suspended in the sludge.
• Many kinds of protozoans are used in the treatment of hazardous wastes. The
type of protozoans used in the activated sludge indicates the overall perfor-
mance of the system. Some of them are listed below:
Table 2 List of Microorganisms (Genus/Family) References

microorganisms playing
Acinetobacter Fredriksson et al. 2012
active role in activated
sludge Akkermansia Yu and Zhang 2012
Prevotella Wells et al. 2014
Acidaminococcus Ivanov et al. 2010
Cloacibacterim Vandewalle et al. 2012
Megasphaera Mazzoli et al. 2007
Moraxellaceae Felföldi et al. 2010
Comamonadaceae Caravelli et al. 2007
Flavobacteriaceae Jin et al. 2011
Rhodocyclacea Phuong et al. 2012
Thiotrichaceacae Yadav et al. 2012
Pseudomonadaceae Childress et al. 2014
1. Amoebae – It has a very little effect on hazardous waste treatment and

dies off instantly as the amount of food decreases.
2. Flagellates – They feed primarily on soluble organic nutrients available in
the sludge.
3. Ciliates – Their function is to clarify water by removing the suspended
bacteria. The crawling ciliates are known to dominate the sludge. This
denotes that the performance of the sludge is good. Presence of the
crawling ciliates is only toward the end of the process.
3. Metazoans
• These groups of microorganisms are set to dominate the older and longer age
systems such as lagoons.
• Metazoans are multicellular organisms, larger than the protozoans. They play
very little role in the removal of the organic material from the treatment
effluent.
• They are also known to feed on the algal and the protozoan population.
• Three common types of metazoan in the activated sludge are as follows:
1. Rotifers – Their basic function is to clarify the effluent. They are the first
group to get affected in presence of toxic loads.
2. Nematodes – Feed on bacteria, protozoans, fungi, and other
nematodes.
3. Tardigrades (water bear) – They are rarely found in the activated sludge.
They are best known to survive in extreme conditions. This particular
group of metazoans are very sensitive to the toxic load.
4. Filamentous bacteria
• Their presence is observed when the operational conditions of the activated
sludge system change drastically.
• Growing in long filaments proves advantageous to them.
• Change in environmental parameters such as temperature, pH, available nutri-

ents such as nitrogen, carbon, phosphorous, etc., brings upon a change in the
activity of these bacteria.
• The dominance of this group in the activated sludge system can pose
problems with sludge settling. As a result, the sludge may become bulky.
The settling efficiency of the bulky sludge is very poor. This results in the
turbid effluent.
• Some filamentous bacteria may cause foaming in the aeration basin and
clarifiers.
5. Algae and fungi
• Their presence is observed with change in pH and age of the sludge.
• They are photosynthetic organisms.
• Their presence denotes poor working condition of the activated sludge.
• It may also indicate the change in the pH or increase in the age of the sludge.
Aerated Lagoon
An aerated lagoon is a type of biological method of treating hazardous wastes. It is a
suspended-growth process in waste treatment unit. The treatment system consists of
a large earthen pond, lagoon, or a basin that is equipped with automated aerators to
sustain an aerobic environment and to prevent the settling of the suspended biomass.
The unit is provided with an inlet and outlet at two different ends to enable the wastes
to flow through it and allow it to be retained for a specific time. Initially, the
population of microorganisms in the aerated environment is much lower than that
in an unaerated setting because there is no scope of sludge recycles. Consequently, a
considerably longer habitation time is required to attain the same waste quality.
However, a longer habitation time may be an improvement when complex organic
compounds are to be degraded simultaneously. Also, the microorganisms in aerated
lagoons are more resilient to process setbacks caused by feed deviations than those in
an unaerated setting because of the larger tank capacities and longer dwelling
times used.
Aerated lagoons are an effective and an economical alternate system for hazard-
ous waste treatment in small populations. They can be incorporated very well into
the surrounding backdrop. If suitable aerators are used, the power input is similar to
an analogous activated sludge plant. In addition to the necessary oxygen transfer, the
aerators have to be provided for proper mixing and circulation. A flow chart of a
typical aerated lagoon system is depicted in Fig. 2.
Fig. 2 An aerated lagoon

system
Lagoons with
Raw waste Treated effluents
aerators
There are two types of aerated ponds:
1. Facultative ponds (common aerated lagoons)

2. Completely mixed aerated ponds
The effluents from the aerated ponds may be recycled or reused. The settled
sludge requires an additional treatment before its proper disposal.
Microorganisms in Aerated Lagoon

Microbes found in aerated and facultative ponds are more varied than those observed
in other hazardous waste treatment processes. This is mainly due to the different
growth parameters present in the surrounding environments. Both aerobic and
anaerobic bacteria are involved along with algae and fungi.
The aerobic bacteria are similar to those found in activated sludge. Four different
groups are found in the aerated lagoon:
(a) Freely distributed

(b) Single cell
(c) Floc-forming bacteria
(d) Filamentous bacteria
All the abovementioned bacteria function likewise in order to oxidize organic

carbon (BOD) to produce carbon dioxide (CO2) and new bacteria.
A number of filamentous bacteria are also present usually when optimum growth
environment is available. Most heterotrophic bacteria function in an extensive range
of environmental parameters. They play a role in removal of BOD over a wide range
of pH and temperature. BOD removal takes place well in a pH range of 6.5–9.0 and
at temperatures ranging from 3–4 C to 65–80 C. Efficiency of BOD removal
declines rapidly below 2–4 C and terminates at 0–2 C.
A very specific group of bacteria occurs to some degree in lagoons that oxidize
ammonia to nitrate. This group of bacteria are strictly aerobes. Two specific bacteria are
involved in nitrification. Further reports suggest that at least five classes of bacteria
oxidize ammonia and at least two of the genera belong to bacteria oxidizing nitrite.
Anaerobic, heterotrophic bacteria commonly occurring in lagoons are mostly
involved in methane production and in sulfate reduction. Anaerobic methane pro-
duction from the lagoons involve two different groups of anaerobic bacteria that
function together to convert organic compounds to methane via a three-step process.
Acid-forming bacteria are diverse group which convert products from the aerated
lagoon under anaerobic conditions to simpler alcohols and organic acids. Examples
of such organic acids are acetic and butyric acid. These bacteria are enduring and
occur over an extensive range of environmental parameters, especially pH and
temperature range.
Anaerobic photosynthetic bacteria occur in almost all aerated lagoons and are
the predominant photosynthetic microorganisms growing in anaerobic condition.
The anaerobic sulfur bacteria are grouped into the red and green sulfur bacteria.
They are represented by above 25 genera. These organisms oxidize the reduced
sulfur compounds (H2S) using the light energy to produce sulfur and sulfate ions.
All the anaerobic photosynthetic bacteria are either strict anaerobes or micro-
aerophilic in nature. Most commonly found are Chromatium, Thiocystis, and
Thiopedia, which grow in abundance and as a result the lagoon appears pink or
red in color. Their presence in the lagoon indicates that there has been an increase in
the organic material load and anaerobic environment in an anticipated aerobic
system. Conversion of the odorous sulfides to its sulfur and sulfate forms by
sulfur-reducing bacteria help significantly in odor control mechanism in many
lagoons (facultative and anaerobic lagoons).
Algae are aerobic organisms. They are photosynthetic in nature. They are capable
of growing in simple inorganic compounds using light as an energy source. These
organisms produce oxygen in the day hours and consume the same in the night
hours. Usually, algal isolates are desirable in lagoons as they help in the generation
of oxygen which is required for the stabilization of the wastes.
There are three major groups of algae. They are characterized based on the color
of the pigment.
(a) Brown algae (diatoms)

(b) Green algae
(c) Red algae
There is one more group that is very common in the lagoons. They are the blue-
green algae, also called as the cyanobacteria. Most of these organisms are capable of
fixing nitrogen. Best studied blue-green bacteria in hazardous waste treatment
systems include Aphanothece, Microcystis, and Anabaena.
Trickling Filter
A trickling filter is a type of waste treatment process consisting of a fixed bed of
rocks, gravel, peat, etc.; they are also referred to as biofilters or biological filter.
They are operated mostly under aerobic condition. Already settled waste water is
continuously sprayed over the filter bed. When the water passes through the pores of
the filter, the organic compounds are degraded aerobically in a continuous process.
Flow chart of trickling bed treatment process is given in Fig. 3.
Rotating Biological Contactors

Rotating biological contactors (RBC), also called rotating biological filters, are
fixed-bed reactors consisting of stacks of rotating disks mounted on a horizontal
shaft. They are partially submerged and rotated as waste flows through. They are
used in conventional wastewater treatment plants as secondary treatment after
primary sedimentation of domestic grey- or blackwater, or any other biodegradable
effluent. The microbial community is alternately exposed to the atmosphere and the
wastewater, allowing both aeration and assimilation of dissolved organic pollutants
and nutrients for their degradation. Flow chart depicting the rotating biological
contactor process is shown in Fig. 4.
Primary Trickling Secondary

Sludge
sedimentation filter sedimentation
To the digester
To primary tank
Fig. 3 Flow chart of trickling bed treatment process
Fig. 4 Flow chart depicting

the rotating biological
contactor process
Rotating
Primary Secondary
biological Effluent
effluent clarifier
contactors
Fig. 5 Flow chart of using

stabilization ponds for the
treatment of hazardous wastes
Feed Anaerobic Stabilization Stabilization
Effluent
storage reactor Pond 1 Pond 2
Stabilization Ponds
Waste stabilization ponds (WSPs) are large, man-made water bodies in which
blackwater, greywater, or fecal sludge are treated by natural occurring processes
under the influence of solar light, wind, microorganisms, and algae. The ponds can
be used individually or linked in a series for improved treatment. Flow chart of using
stabilization ponds for the treatment of hazardous wastes in shown in Fig. 5.
There are three types of ponds
(1) Anaerobic ponds
(2) Facultative ponds
(3) Aerobic ponds
BOD and pathogen removal is high. But, large surface areas and expert design are
required. The effluent still contains nutrients and is therefore appropriate for the
reuse in agriculture, but not for direct recharge in surface waters.
Packed Bed Reactors

Packed bed reactors can be used in chemical reaction. These reactors are tubular and
are filled with solid catalyst particles, most often used to catalyze gas reactions. The
chemical reaction takes place on the surface of the catalyst. The advantage of using a
packed bed reactor is the higher conversion per weight of catalyst than other catalytic
reactors. The conversion is based on the amount of the solid catalyst rather than the
volume of the reactor.
Bioremediation
Bioremediation is not only a process of removing the pollutant from the environment
but also is an eco-friendly and more effective process. The pollutants can be removed
or detoxified from the soil and water by the use of microorganisms, known as
bioremediation. The purpose of bioremediation is to make environment free from
pollution with the help of environmental friendly microbes. Bioremediation can be
broadly divided into two categories, i.e., in situ bioremediation and ex situ bioreme-
diation (Singal et al. 2000; Singh et al. 2009).
In situ bioremediation provides the treatment at contaminated sites avoiding
excavation and transport of contaminants. There is a biological treatment for
cleaning the hazardous substances on the surface. It involves the use of oxygen
and nutrient in the contaminated site in the form of aqueous solution in which
bacteria grow and help to degrade the organic matter. It can be used for soil and
groundwater (Gupta and Mohapatra 2003; Gosavi et al. 2004).
Generally, this technique includes conditions such as the infiltration of water
containing nutrients and oxygen or other electron acceptors for groundwater treat-
ment. Most often, in situ bioremediation is applied to the degradation of contami-
nants in saturated soils and groundwater. It is a superior method to cleaning
contaminated environments since it is cheaper and uses harmless microorganism
to degrade the chemicals. Chemotaxis is important to the study of in situ bioreme-
diation as microorganisms with chemotactic abilities can move into an area
containing contaminants. So, by enhancing the cells’ chemotactic abilities, in situ
bioremediation will become a safer method in degrading harmful compounds
(Rahuman et al. 2000).
In situ bioremediation is further subdivided into following categories
(a) Bioventing
(b) Biostimulation
(c) Biosparging
(d) Fixed biobarriers/biowalls
(e) Bioaugmentation
(f) Phytoremediation
(g) Constructed/artificial wetland
Ex situ bioremediation is further subdivided into following categories
(a) Landfarming
(b) Composting
(c) Biopile/Biocells/Bioheap
(a) Bioventing
Bioventing is an in situ treatment, which is a combination of oxygen (O2) and

nutrients along with vapor extraction. It is a technique used to degrade any aerobi-
cally degradable compound. In bioventing, the oxygen and nutrients like nitrogen
and phosphorus are injected into the contaminated site. The distribution of these
nutrients and oxygen in soil is dependent on soil texture. Bioventing is pumping of
air into contaminated soil above the water table through well. Enough oxygen is
provided through low air flow rate for the microbes. Bioventing is more effective if
the water table is deep from the surface and the area having high temperature. It is
mainly used for the removal of gasoline, oil, petroleum, etc. The rate of removal of
these substances varies from site to site due to the differences in the soil texture and
the composition of hydrocarbons. (Singh and Tripathi 2007; Strong and Burgess
2008)
(b) Biostimulation
Biostimulation refers to the modification of contaminated areas to enhance the

growth of indigenous microbes already present. This process may include utilizing
fertilizers and other nutrients to stimulate the microbes.
(c) Biosparging
This approach aims to increase biological activity of the soil by increasing the O2
supply. Air is initially injected through wells, after pure O2 is injected. In
biosparging, air is injected below the ground water under pressure to increase the
concentration of oxygen. The oxygen is injected for microbial degradation of
pollutant. Biosparging increases the aerobic degradation and volatilization. There
must be control of pressure while injecting the oxygen at the contaminated site to
prevent the transfer of volatile matter into the atmosphere. The cost can be reduced
by decreasing the diameter of injection point. Before injecting the oxygen the soil
texture and permeability is analyzed. This technology is applied to a known source
of gasoline contamination in order to quantify the extent of remediation achieved in
terms of both mass removed and reduction in mass discharge into groundwater.
Heavier products (e.g., lubricating oils) generally take longer period to biodegrade
than the lighter products, but biosparging can still be used at these sites (Vidali 2001;
Lambert et al. 2009).
(d) Fixed Biobarriers/Biowalls
Fixed biobarriers use solid or viscous amendments placed across the flow path of
contaminated groundwater to form a permeable reactive barrier. The fixed biobarrier
approach can use engineered trenches or barriers containing solid phase, slow-
release substrates or viscous substrates placed cross gradient via direct-push injec-
tions. In situ enhanced bioremediation in the form of a fixed biobarrier is a suitable
technology for large plumes having poorly defined, widely distributed, or inacces-
sible source areas (Funari et al. 2016).
(e) Bioaugmentation
Bioaugmentation refers to the addition of naturally occurring microbes to con-

taminated materials and sites in order to achieve bioremediation. The process
ensures that the suitable microbes are added in sufficient quantities. Microorganisms
having specific metabolic capability are introduced to the contaminated site for
enhancing the degradation of waste. At sites where soil and groundwater are
contaminated with chlorinated ethenes, such as tetrachloroethylene and trichloro-
ethylene, bioaugmentation is used to ensure that the in situ microorganisms can
completely degrade these contaminants to ethylene and chloride, which are non-
toxic. Monitoring of this system is however difficult (Niu et al. 2009).
(f) Phytoremediation
Phytoremediation is the use of plants for removal of contaminants from soil or

water. Contaminants are fixed in the ground, accumulated in the plant tissue, or
released to the atmosphere.
Phytoremediation consists of four different plant-based technologies each having
a different mechanism of action for the remediation of soil polluted with heavy
metals or water. These technologies comprise (Cobbett 2000; Cobbett and
Goldsbrough 2002):
(a) Rhizofiltration: It involves the use of plants to remediate aquatic environments.

(b) Phytostabilization: It involves stabilization of polluted soil by using plants.
(c) Phytovolatilization: Involves the use of plants to extract metals from the soil and
then releasing them into the atmosphere by volatilization and
(d) Phytoextraction: It involves the use of plants to absorb metals from the soil
followed by translocation in the harvestable shoots.
The main physiological steps in phytoremediation include:
(a) Stimulation of microorganism-based transformation by plant exudates

(b) Slowing of contaminant transport from the vegetated zone due to adsorption and
increased evapo-transpiration
(c) Plant uptake, followed by metabolism or accumulation
Fig. 6 Uptake mechanism of pollutants and other wastes by phytoremediation process
Phytoremediation is an interdisciplinary technology that can benefit from many

different approaches. Results already obtained have indicated that some plants can
be effective in toxic metal remediation. The processes that affect metal uptake,
availability, translocation, degradation, chelation, and volatilization need to be
investigated in detail. Uptake mechanism of pollutants and other wastes by
phytoremediation process is given in Fig. 6.
(g) Constructed/Artificial Wetlands
Wetlands constructed for remediation purposes are examples of

phytoremediation. Constructed wetlands have been used for decades for the man-
agement and treatment of many wastewaters, including municipal, acid mine drain-
age, agriculture, petrochemical and textile industries, and storm water. However,
constructed wetlands are being used for the remediation of groundwater for surface
water impacted by industrial chemicals and wastes such as landfill leachate and
explosives such as 2,4,6-trinitrotoluene (TNT) or 1,3,5-trinitro-1,3,5-triazinane
(RDX). The trend towards increased use of constructed wetland technology relates
to the low capital cost on operating and maintaining the passive technology.
Ex Situ Bioremediation
The treatments are not given at site. In ex situ, the contaminated soil is excavated and
treated at another place. This can be further subdivided into following categories:
(a) Land Farming
Landfarming refers to a “low tech” biological treatment which involves the

controlled application and spread-out of a more-or-less defined organic bioavailable
waste on the soil surface, and the incorporation of the waste into the upper soil zone.
It is typically used for biological removal of petroleum products from contaminated
soil. In land farming make a sandwich layer of excavated soil between a clean soil
and a clay and concrete. The clean soil at bottom and concrete layer should be the
upper most layers. After this, allow it for natural degradation by providing oxygen,
nutrition, and moisture. pH should be maintained at 7 by using lime. Land farming is
also useful for pesticides contaminated sites.
Land farming is a bioremediation technology. Contaminated soils are mixed with
soil amendments such as soil bulking agents and nutrients, and then they are tilled
into the earth. The material is periodically tilled for aeration. Contaminants
are degraded, transformed, and immobilized by microbiological processes and by
oxidation. Soil conditions are controlled to optimize the rate of contaminant degra-
dation. Moisture content, frequency of aeration, and pH are all conditions that may
be controlled. Land farming differs from composting because it actually incorporates
contaminated soil into soil that is uncontaminated. Composting also generally takes
place in aboveground piles (Maila and Cloete 2004).
(b) Composting
Due to its common use for household garden waste, this is the well-known
controlled biological decomposition of organic material in the presence of air to
form a humus-like material. Methods of composting include mechanical mixing and
aerating, ventilating the materials by dropping them through a vertical series of
aerated chambers, or placing the compost in piles out in the open air and mixing it or
turning it periodically. Compositing is a process in which microorganism degrades
the waste at elevated temperature that ranges from 55 to 65 C. During the process of
degradation, microbes release heat and increase the temperature which leads to more
solubility of waste and higher metabolic activity in composts.
In composting rocks and other larger particles are removed from excavated
contaminated soil. The soil is transported to a composting pad with a temporary
structure to provide containment and protection from weather extremes. Amend-
ments (straw, alfalfa, manure, agricultural wastes, and wood chips) are used for
bulking agents and as a supplemental carbon source. Soil and amendments are
layered into long piles known as windrows.
Wastes are two type, i.e., inorganic waste and organic waste. The inorganic waste
includes mainly heavy metals and organic waste includes agricultural waste, plastics,
rubbers, etc.
Researchers have found a variety of the ways by which we can degrade the solid
waste. But bioremediation makes its leap to tackle the problem of heavy metals
associated with different categories of waste with the help of microorganism.
(c) Biopile/Biocells/Bioheaps
It is a hybrid of composting and land farming. The basic biopile system includes a
treatment bed, an aeration system, an irrigation/nutrient system, and a leachate
collection system. For proper degradation, there should be control of moisture, heat,
nutrients, oxygen, and pH. The irrigation system is buried under the soil. Air and
nutrients are provided through vacuum. To prevent the run off, the soil is covered
with plastic and due to which evaporation and volatilization is also prevented and
promote solar heating. Biopile treatment takes 2 to 3 months to complete the
procedure.
Factors that may limit the applicability and effectiveness of the process include:
• Digging of contaminated soils is required.

• Treatability testing should be conducted to determine the biodegradability of the
contaminants and appropriate oxygenation and nutrient loading rates.
• Solid phase processes have questionable effectiveness for halogenated com-
pounds and may not be very effective in degrading transformation products of
explosives.
• Similar batch sizes require more time to complete cleanup than slurry phase
processes.
• Static treatment processes may result in less uniform treatment than processes that
involve periodic mixing.
Organisms Used in Bioremediation

As stated previously, bioremediation involves various microorganisms that are able
to degrade and reduce toxicity of environmental pollutants. Therefore, the interac-
tions of microbes with the environment and pollutants are significant in determining
effectiveness of bioremediation. Those microbes can be either naturally present in
the site of bioremediation or isolated from other sites and inoculated artificially.
Biodegradation often occurs as part of microbial metabolism and in some cases,
microbes are able to directly harvest carbon and energy by breaking down pollutants.
Sections below go over bacteria and fungi, the commonly used organisms in
bioremediation, and archaea, the more recently discovered group of organisms
with unique potential in bioremediation.
Bacteria
Bacteria are widely diverse organisms, and thus make excellent players in biodeg-
radation and bioremediation. There are few universal toxins to bacteria, so they
are likely to break down any given substrate, under optimum conditions (anaerobic
vs. aerobic environment, sufficient electron donors or acceptors, etc.). Below are
several specific bacteria species known to participate in bioremediation.
(i) Pseudomonas putida: Pseudomonas putida is a Gram-negative soil bacterium

that is involved in the bioremediation of toluene, a component of paint thinner.
It is also capable of degrading naphthalene, a product of petroleum refining, in
contaminated soils.
(ii) Dechloromonas aromatica: Dechloromonas aromatica is a rod-shaped bacte-
rium which can oxidize aromatics including benzoate, chlorobenzoate, and
toluene, coupling the reaction with the reduction of oxygen, chlorate, or nitrate.
It is the only organism able to oxidize benzene anaerobically. Due to the high
propensity of benzene contamination, especially in ground and surface
water, D. aromatica is especially useful for in situ bioremediation of this
substance.
Nitrifiers and Denitrifiers

Industrial bioremediation is used to clean wastewater. Most treatment systems rely
on microbial activity to remove unwanted mineral nitrogen compounds (i.e., ammo-
nia, nitrite, and nitrate). The removal of nitrogen is a two-stage process that involves
nitrification and denitrification. During nitrification, ammonium is oxidized to nitrite
by organisms like Nitrosomonas europaea. Then, nitrite is further oxidized to nitrate
by microbes like Nitrobacter hamburgensis.
In anaerobic conditions, nitrate produced during ammonium oxidation is used as
a terminal electron acceptor by microbes like Paracoccus denitrificans. The result is
N2 gas. Through this process, ammonium and nitrate, two pollutants responsible for
eutrophication in natural waters, are remediated.
(i) Deinococcus radiodurans: Deinococcus radiodurans is a radiation-resistant

extremophile bacterium that is genetically engineered for the bioremediation of
solvents and heavy metals. An engineered strain of Deinococcus radiodurans
has been shown to degrade ionic mercury and toluene in radioactive mixed
waste environments.
In anaerobic conditions, nitrate produced during ammonium oxidation is used
as a terminal electron acceptor by microbes like Paracoccus denitrificans.
The result is dinitrogen gas. Through this process, ammonium and nitrate,
two pollutants responsible for eutrophication in natural waters, are remediated.
(ii) Methylibium petroleiphilum: Methylibium petroleiphilum (formally known as
PM1 strain) is a bacterium capable of methyl tert-butyl ether (MTBE) biore-
mediation. PM1 degrades MTBE by using the contaminant as the sole carbon
and energy source.
(iii) Alcanivorax borkumensis: Alcanivorax borkumensis is a marine rod-shaped
bacterium which consumes hydrocarbons, such as the ones found in fuel, and
produces carbon dioxide. It grows rapidly in environments damaged by oil, and
has been used to aid in cleaning the more than 830,000 gallons of oil from
the Deepwater Horizon oil spill in the Gulf of Mexico
Fungi (Mycoremediation)
Current bioremediation applications primarily utilize bacteria, with comparatively
few attempts to use fungi. Fungi have fundamentally important roles because of their
participation in the cycling of elements through decomposition and transformation of
organic and inorganic materials. These characteristics can be translated into appli-
cations for bioremediation which could break down organic compounds and reduce
the risks of metals. In some cases, fungi have an advantage over bacteria not just in
metabolic versatility but also their environmental flexibility. They are able to oxidize
a diverse amount of chemicals and survive in harsh environmental conditions such as
low moisture and high concentrations of pollutants. Therefore, fungi are potentially
an extremely powerful tool in soil bioremediation and some versatile species such as
white rot fungi have been a hot topic of research.
(i) Phanerochaete chrysosporium
P. chrysosporium was the first fungi linked to degradation of organic pollutants.

Extensive research has shown that it has strong potential for bioremediation in
pesticides, PAHs, dioxins, carbon tetrachloride, and many other pollutants. Among
fungal systems, P. chrysosporium has become the model for bioremediation. Other
notable species of white rot fungi include Pleurotus ostreatus and Trametes
versicolor.
Archaea
The role of archaea in bioremediation has not been studied as commonly as that of
bacteria. Nevertheless, numbers of researchers have shown their ability to degrade
various pollutants and scientists began to discover more about their potential in
participating in bioremediation. Below are lists of some important facts regarding
archaea’s potential role in bioremediation.
– Hydrocarbon-contamination is observed in some extreme environments, includ-

ing hypersaline (high salt concentration), high or low temperature, or extreme
pH. Archaea’s adaptation to extreme environment gives them the potential to
participate in biodegradation and bioremediation in these environments; in fact,
microorganisms naturally adapted to the cold environments are known to be
important degraders of hydrocarbons in those environments.
– Extreme halophilic archaea has potential to biodegrade pollutants in hypersaline
environment, in which bacteria typically used in bioremediation cannot survive or
function properly.
– Some archaea are known to be resistant to variety of antibiotics, including
penicillin, cycloheximide, streptomycin, etc., which gives them great advantage
in participating in bioremediation in the presence of antibiotics.
Examples of studies of Archaea involved in bioremediation:

Four extreme halophilic strains of archaea (belonging to genus Halobacterium,
Haloferax, and Halococcus) were studied to evaluate their potential to degrade crude
oil and hydrocarbons (Singh and Tripathi 2007). All four strains could use various
kinds of hydrocarbons as their carbon or energy sources. Two strains of Haloferax
grew on n-alkanes with different lengths, ranging from C8 to C34, and also benzene,
toluene, biphenyl, and naphthalene. The research demonstrated the important fact
that archaea have potential to carry out biodegradation at high temperatures, in the
range of 40–45 C, which is advantageous as hydrocarbons have higher solubility
and bioavailability at these higher temperature. The four strains studied were
resistant to six different antibiotics, including penicillin, streptomycin, and cyclo-
heximide, and this gave them the potential to carry out biodegradation in conditions
unfavorable for bacteria. Research suggests other genera of archaea are also capable
of biodegrading in hypersaline environments. Archaeglobus fulgidus, a hyperther-
mophile that can use sulfate as an electron acceptor, can also break down various
aromatic hydrocarbons. Microorganisms used for the bioremediation process has
been listed in table below.
Bioremediation of Hydrocarbon Pollutants

Hydrocarbons are stored deep underground but are brought up to the surface to be
transformed and utilized, primarily as an energy source known as fossil fuels. The
majority of pollution currently comes from these by-products in the form of poly-
cyclic aromatic hydrocarbons (PAHs), which are xenobiotic environmental pollut-
ants that form when carbon materials are incompletely combusted. Some of
examples of PAHs include burning wood, fossil fuels, and cigarette smoke. Cur-
rently, bioremediation is only effective for soils contaminated with low-molecular
weight PAHs because of bacterial commercial use. However, fungi are effective at
PAH degradation in comparison to bacteria for few reasons (Blanca et al. 2007).
Firstly, they are capable of degrading PAH’s that are high in molecular weight;
bacteria in comparison are better at degrading smaller molecules. Secondly, fungi
can function well in nonaqueous environments and low oxygen conditions, both are
conditions where PAH’s can accumulate. Many fungi have evolved mechanisms that
allow them to target specific PAHs. Fungi produce extracellular enzymes that
degrade lignin, a process called mineralization that produces carbon dioxide as the
end product. The different methods of bioremediation used by the microorganisms
for degrading pollutants have been listed in Table 3.
Remediating Metals
Toxic metals can enter the environment at all life cycle stages of metal compound. For
example, metal leaching can occur from the mining process till the disposal of metal
wastes. However in nature, the mobility of metals comes from the geological processes
that can be released into the soil and aquatic environments. The environmental largest
risk from metal contamination comes from the relationship between metals and com-
pounds that are inherently of incapable of being degraded by any natural procedures.
The best solution to treating contamination is transporting the metals to location where
they cannot produce negative environmental effects. Fungi have various ways of
interacting with metals; some of the techniques are increasing or decreasing the
mobility of metals, sorption, or even cellular uptake. After the metals have been
absorbed by the fungus, they can be chemically altered to be stored or translocated
through the hyphae into various plants that participate in symbiosis.
Pesticide Degradation
Pesticide accumulation is an issue of great concern among the public, because
they are directly associated with food products and water supplies. There are
number of technologies used for pesticide cleanup; however, these technologies
are generally expensive and inefficient because they require contaminated soil to
be excavated and sent to a separate storage location for processing. Bioremedia-
tion offers a potential solution that treats contaminated soil and groundwater
Table 3 The different methods of bioremediation used by the microorganisms for degrading
pollutants
Pollutants Organisms Function
2,2,6- Trinitrotoluene (TNT) Methanococcus sp. Biotransformation
Atrazine Pseudomonas sp. (ADP) Biodegradation
Chlorpyrifos Enterobacter strain B-14 Biodegradation
Dibenzothiophene (DBT) Rhizobium meliloti Biodegradation
Hexahydro-1,3,5-trinitro-1,3,5-triazine Acetobacterium paludosum Biodegradation
(RDX)
PAHs Pseudomonas sp. Biodegradation
Pycnoporus sanguineus
Coriolus versicolor
Pleurotus ostreatus
Fomitopsis palustris
Daedalea elegans
Rhizobium sp.
Phenanthrene, PAH Agrobacterium sp. Biodegradation
Bacillus sp.
Burkholderia sp.
Polychlorinated biphenyl (PCB) Rhodococcus erythropolis Biodegradation
TA421
Rhizobium sp.
Polycyclic aromatic hydrocarbon (PAH) Fungi Biodegradation
without needing excavation. Studies show that white rot fungi has high promise
for soil bioremediation application; however, most tests have been conducted in
the lab rather than in the actual environment. This fungus demonstrates the ability
to transform and mineralize specific pesticides in soil.
Environmental Applications
Although fungi demonstrate significant biochemical and ecological useful qualities,
they are hardly utilized for biotechnological purposes. Instead, bacteria are most
commonly used because they usually produce superior results in their numerous
advantages ranging from their highly specific biochemical reactions to their capabilities
of breaking down pollutants efficiently. Fungi are underused primarily because of the
costs that come from providing oxygen to fungi in polluted environments. However,
filamentous fungi could be highly valuable in situations where bacteria cannot perform.
For example, fungi are useful in situations where contaminants are physically block-
aded and bacteria cannot reach or in circumstances of environmental extremes such as
high acidity or dryness prevent bacteria from functioning.
Limitations of Treating Hazardous Wastes Using the Biological

Treatment Method
Some common environmental limitations to biodegradation are related to hazardous

chemical wastes which possess high waste concentrations and toxicity. Because
some time this toxicity either inhibits the growth of microorganism or even kill
them. For proper growth of microorganism, it requires favorable pH condition,

sufficient amount of mineral nutrients and temperature on which maximum microbes
can survive, i.e., 20 C–30 C. Once the limitations by environmental conditions are
corrected, the ubiquitous distribution of microorganisms, in most cases, allows for a
spontaneous enrichment of the appropriate microorganisms. In the great majority of
cases, an inoculation with specific microorganism is neither necessary nor useful.
Besides other factors also affect bioremediation such as solubility of waste, nature
and chemical composition of waste, oxidation-reduction potential of waste, and
microbial interaction. Hence, researchers should search genetically different type
of microbes which can also work on slightly adverse conditions. Therefore, biore-
mediation is still considered as a developing technology to regulate the day-to-day
environmental problems faced by men residing in an area.
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Part IV
Management of Radioactive Wastes
30
Bouchra El Hilal, Mohammed Hussein Rafeq Khudhair, and
Ahmed El Harfi
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 745
Notions of Radioactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 746
The Laws of Radioactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 747
Radioactive Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 747
Radioactive Decay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 748
Radioactive Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 748
Classification of Radioactive Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 749
Radioactive Waste Management: Case of Morocco . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 749
International Obligations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 752
Purpose of National Radioactive Waste Management Policy and Scope . . . . . . . . . . . . . . . . . . . . . . 753
Policy Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 753
Long-Term Management of RW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 754
General Principles of the Morocco Policy for Radioactive Waste Management . . . . . . . . . . . . . . 755
Organizational Framework and Allocation of Responsibilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
National Council for Nuclear Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
B. El Hilal (*)
Laboratory of Agro resources Polymers and Process engineering (LAPPE), Team of
Macromolecular and Organic Chemistry, Faculty of sciences, Ibn Tofail University,
Kenitra, Morocco
Operation Unit of the Radioactive Waste, Center of Nuclear Studies of Maamora (CENM)
(CNESTEN), Kenitra, Morocco
M. H. R. Khudhair
Kenitra, Morocco
Laboratory of Chemistry of Solid State, Faculty of Science, Ibn Tofail University, Kenitra, Morocco
A. El Harfi
Kenitra, Morocco

https://doi.org/10.1007/978-3-319-73645-7_83
744 B. El Hilal et al.
Establishing a New Unified and Independent Regulatory Body . . . . . . . . . . . . . . . . . . . . . . . . . . . 758

Defining Role of Operators and Organization Responsible for Centralized and
Long-Term Radioactive Waste Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 758
National Strategy for Radioactive Waste Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 760
Disused Sealed Radioactive Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 760
Strategic National Framework for Radioactive Waste Management . . . . . . . . . . . . . . . . . . . . . . . . . . . 762
Monitoring Strategy Implementation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 762
Updating the Strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
National Model for Radioactive Waste Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
Waste Generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
Predisposal Management of Radioactive Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
Waste Management End Points . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 764
Long-Term Waste Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 765
Management of Disused Sealed Radioactive Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 765
Management of Spent Radioactive Ion Exchange Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 766
National Process for Implementing the Radioactive Waste Management Strategy . . . . . . . . . . . . 767
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 769
Abstract
The radioactivity is a natural phenomenon and natural sources of radiation
present in the environment. Radiation and radioactive substances have many
useful applications, ranging from power generation to medical, industrial, and
agricultural applications. At the end of their use, the radioactive elements
containing in the used materials (radioactive waste) cannot be destroyed by any
known chemical or mechanical process. Their final destruction is the fact either of
a transformation into stable isotopes by radioactive decay or of a nuclear trans-
mutation under the effect of the bombardment of atomic particles. The manage-
ment of the radioactive waste, therefore, consists of controlling radioactive waste
and maintaining it at a tolerable level in order to control the risks presented to man
and his environment. The stakes of the management of radioactive waste are
therefore of several kinds, technical and scientific, but also political and ethical;
the fact that certain wastes generated pose safety problems in the very long term
because their harmfulness can extend over very long periods of time.
Keywords
Radioactve waste · Management of radioactive wastes · Radioactivity ·
Radioactive decay · Classification of radioactive waste · Disposal · Quality
management system ion exchange resins · Radiological ris · Exempted waste ·
Very short lived waste · Very low level waste · Low level waste · High level
waste · Low and intermediate level waste · Waste minimization · Safety and
security
Abbreviations
CENM Centre d’Etudes Nucléaires de la Maâ mora
CGEM General Confederation of Moroccan Companies
CNEN Conseil National de l’Energie Nucléaire
30 Management of Radioactive Wastes 745
CNESTEN Centre National de l’Energie, des Sciences et des Techniques

Nucléaires
CNRP Centre National de Radioprotection
CNSN Commission Nationale de Sûreté Nucléaire
DSRS Disused sealed radioactive sources
EW Exempt waste
IAEA International Atomic Energy Agency
LLW Low level waste
MEMEE Ministère de l’Energie, des Mines, de l’Eau et de l’Environnement
(Ministry of Energy, Mines, Water and Environment)
MoH Ministry of Health (Ministère de la Santé)
NORM Naturally occurring radioactive materials
NRSSA Nuclear and Radiological Safety and Security Agency (Agence de
Sûreté et de Sécurité Nucléaires et Radiologiques)
QMS Quality Management System
RAIS Regulatory Authority Information System
RW Radioactive waste
RWM Radioactive Waste Management
SNF Spent nuclear fuel
TENORM Technologically enhanced naturally occurring radioactive
materials
TSO Technical support organization
VLLW Very low level waste
VSLW Very short lived waste
WHO World Health Organization
WMO Waste Management Organization
Introduction
Most human enterprises produce waste, some of which is radioactive (Ojovan et al.
2013; Venturini 2010; Giusti 2009). Radioactive waste contains materials that emit
ionizing radiation, which has been recognized as a potential hazard to human health
since the beginning of the twentieth century. The safe management of radioactive
waste is therefore essential for the protection of human health and the environment,
in the present and future (Jorda and Forest 1999).
Radioactive waste is produced during the operational and decommissioning
phases of facilities associated with the following activities:
• Operation of the nuclear reactor and other facilities within the nuclear fuel cycle.
• Production and use of radioactive materials in the fields of scientific research,
medicine, industry, agriculture, trade, and education.
• Extraction, isolation, and treatment of raw materials (such as oil, gas, and other
strategic industries) containing naturally occurring radioactive materials (NORM).
• Secondary radioactive waste resulting from the management of waste.
• Disused or spent radioactive resources.
Radioactive waste may occur in a gaseous, liquid, or a solid form that may range
from low radioactivity (for example, medical waste, laboratory waste, and certain
mining wastes) to highly radioactive waste (for example, spent nuclear fuel and
certain spent radioactive sources). The physical and chemical characteristics of the
various wastes (e.g., the activity concentration, half-life, mixture of radioactive
nuclides, chemical toxicity, and radiotoxicity) vary widely. Radioactive waste may
also occur together with other hazardous chemical or biological materials. The levels
of radiation associated with radioactive waste should be seen in perspective to the
natural background radiation to which everyone is exposed in everyday life.
Radioactive wastes generated by facilities range from low volumes, such as spent
radioactive sources, to large and diffuse volumes, such as legacy decommissioning
waste or NORM materials from mining, and their radioactive decay products.
In Morocco, the use of sealed or nonsealed radioactive sources in solid or liquid
form in the healthcare sectors (radiodiagnostics, nuclear medicine, radiotherapy, etc.),
industry (gamma radiography, level gauges, or tracers), agriculture (sterilization or
conservation of products), mines, and other (teaching and research) is the source
of the production of radioactive waste of various kinds and form (liquid or solid).
Notions of Radioactivity
All the bodies of nature consist of atoms or assemblies of atoms. An atom is the
smallest amount of an element that can combine to form a molecule or crystal
structure (Zaitar 2012). The atom consists of:
• A central nucleus made up of an assembly of protons and neutrons.

• A peripheral cloud composed of a series of electrons.
The nucleus (or nucleus of atom) is characterized by the total number of its
nucleons A, called mass number, and by the number of its protons Z, called the
atomic number. Most nuclei of atoms are naturally stable (Fig. 1)
The arrangement of nucleons within the nucleus results from a balance between
electrostatic repulsive forces that tend to spread protons and attractive forces with very
short radii that tend to bring the nucleons closer together. The radioactivity results
from an imbalance between these forces, due to an excess of either neutrons or protons
or both (Horowitz 1952; Radvanyi and Bordry 1984; Boudia 2001; Curie and Curie
1899; Douce and Guillot-Salomon 1970; Joliot and Curie 1934). Two nuclides are
isotopes if they have the same atomic number Z but different numbers of masses A.
An isotope, when it is radioactive, is called a radionuclide or radioisotope. The
chemical properties of radioactive isotopes are the same as those of stable isotopes.
One element may thus have radioactive isotopes and nonradioactive isotopes (Fig. 2).
The hydrogen atom has two isotopes: deuterium and tritium. The electrical charge
of the three cores as well as the chemical properties are identical. Deuterium is stable,
as for tritium, it is unstable and radioactive.
Fig. 1 Illustrative diagram of

an atom (Zaitar 2012)
Neutron
Proton
Electron
Fig. 2 The different isotopes L’Hydrogène 1H Le deutérium 2H ou D Le tritium 3H ou T

of the hydrogen atom
Noyau : 1 électron Noyau : 1 électron Noyau : 1 électron

1 proton 1 proton 1 proton
1 Neutron 2 Neutrons
The Laws of Radioactivity
Radioactive Activity
Radioactive activity is the number of disintegrations that occur per unit time in a
given amount of the radionuclide that constitutes it (Zaitar 2012), expressed as:
AðtÞ ¼ λ NðtÞ
Or
λ is the radioactivity constant, characteristic of the element under consideration.
The unit is Becquerel (Bq): equal to one decay per second.
Fig. 3 Radioactive decay N
N0
N( t ) = N0 e –λt
N0
2
t 1/ t
2
Radioactive Decay
The radioactive decay of a given nucleus is a random phenomenon. On the other

hand, the calculation of the probability makes it possible to know with precision the
number of nuclei that will transform per unit of time (Devillers et al. 1975; Zaitar
2012; Braham et al. 1979; Vieu et al. 1973).
dN ¼ λ N dðtÞ
If one knows the activity of the radionuclide and the number of atoms present N0,
one can then deduce the number of remaining atoms Nt as a function of the time
elapsed:
Nt ¼ N0 eλt
This is the radioactive decay, which is therefore an exponential function of time.

However, for each radionuclide a radioactive period T is defined at the end of which
half of the radioactive atoms disappear by spontaneous transformation (Fig. 3).
Nt=N0 ¼ eλt ¼ ½etlog2 ¼ λT

T ¼ log2=λ
Radioactive Waste
The International Atomic Energy Agency (IAEA) defines radioactive waste as “any
material for which no use is foreseen and which contains radionuclides in concen-
trations above the values that the competent authorities consider to be permissible
materials in materials suitable for noncontrolled use” (International Atomic Energy
Agency 2002, 2008, 2011).
Classification of Radioactive Waste
Safe management of radioactive waste depends on knowledge of its characteristics

and characterization may occur in several stages. Knowledge of the origin of the
waste provides the first indication of its characteristics; direct measurements and
observations then improve or confirm this information. The aim of characterization
is to define the properties sufficiently to allow the waste to be accepted for successive
waste management steps and ultimately to meet waste acceptance criteria for the
disposal facility.
Waste generators have responsibility for characterizing the wastes they generate.
The regulatory body must be satisfied that this has been performed adequately.
Demonstration of an adequate characterization regime is aided by the application
of a quality management system (QMS) that produces, for each waste package,
records that are reliable, traceable, and retrievable. The QMS will also include
training, method development, qualification, and documentation.
Remembering that radioactive waste is an industrial product, there is a possibility
that it may contain hazardous substances that are nonradioactive. Disposal of such
substances will need to satisfy environmental legislation, which means that they too
should be considered during waste characterization.
The table below identifies the radioactive waste classification scheme (Table 1).
Radioactive Waste Management: Case of Morocco
As a Member State of the IAEA and a Party to the Joint Convention on the Safety of
Spent Fuel Management and the Safety of Radioactive Waste Management, the
Kingdom of Morocco Country is committed to managing radioactive waste in a safe,
secure and sustainable manner in accordance with internationally recognized prin-
ciples related to nuclear and radiation safety. The application of those principles aims
to ensure adequate protection of workers, the general public and the environment,
now and in the future, from the harmful effects of ionizing radiation. Requirements
for nuclear and radiation safety apply to all types of radioactive waste present in the
country, regardless of their physical and chemical characteristics or origin, at all
stages of their management. Compliance with International Standards implies in
particular the implementation of ICRP recommendations on radiation protection and
the application of Fundamental Safety Principles as specified in IAEA Safety
Publications.
In addition to matters of safety, the Kingdom of Morocco is also committed to
establishing a beneficial, responsible, and sustainable RWM system in accordance
with the IAEA Nuclear Energy Basic Principles and Fundamental Safety Principles.
When applied to the management of radioactive waste and spent nuclear fuel, these
require:
• Minimization of generation and optimization of the management of radioactive

waste
750
Table 1 The radioactive waste classification scheme

Waste type Waste class Waste origin Waste criteria Management/disposal options
Liquid Exempted waste (EW) Various sources Annual dose to population Released to the environment
>10 μSv
Very short lived waste Reactors, research institutions, medical Activity<37kBq/m3 Clearance or authorized discharge
(VSLW) institutions, universities, and industry after decay storage
Very low level waste Decommissioning waste, medical 3.7kBq/m3<Activity Solidification with further
(VLLW) institutions, research institutions, <3.7MBq/m3 management according to the waste
operation of nuclear facilities, uranium type “solid” (see below)
mining and milling
Low level waste (LLW) Decommissioning waste, isotope 3.7GBq/m3>Activity Solidification with further
production, fuel fabrication, >37MBq/m3 management according to the waste
enrichment, reprocessing of spent T1/2<30 years type “solid” (see below)
nuclear fuel
Organic low and Research processes, reactors, spent Contains organics Solidification with further
intermediate level waste nuclear fuel management according to the waste
(OLILW) type “solid” (see below)
High level waste Contamination from damaged spent Contact dose rate > 2 mSv/ Solidification with further
(HLW) nuclear fuel h, no long-lived management according to the waste
radionuclides type “solid” (see below), or deep
borehole injection
Solid EW Various sources Annual dose for Released to environment
population>10 μSv
VSLW Research and medical institutions T1/2 < 100 day Clearance or authorized discharge
after decay storage
B. El Hilal et al.
30
VLLW Decommissioning waste, medical Alpha activity up to Temporary storage and near-surface
institutions, research institutions, 400 Bq/g disposal (e.g., shallow trench/landfill)
operation of nuclear facilities, uranium Gamma and beta activity
mining and milling up to 4 kBq/g
Low and intermediate Decommissioning waste, uranium 400 Bq/g < Alpha Near-surface disposal (e.g.,
level waste (LILW) mining and milling, isotope activity < 4 kBq/g engineered)
production, fuel fabrication, 4 kBq/g < Gamma and
enrichment, reprocessing of spent beta activity < 40 kBq/g
nuclear fuel, filters
HLW Heat-generating waste, fission 104 to 106TBq/m3 Geological disposal (medium or deep)
products, actinides, spent nuclear fuel or
(if declared as waste) Activity levels higher than
that of LILW
or
Intrusion dose greater than

100 mSv/y
Disused sealed Short-lived Nondestructive examinations, level 0.27 mCi–270 mCi Near-surface disposal (e.g.,
radioactive sources measures engineered)
(DSRS) Long-lived Well-logging 270 mCi–270 Ci Geological disposal (medium or
deep), borehole disposal
Spent high activity Radiators, telemedicine, gamma knife 270 Ci–270kCi Deep geological disposal, borehole
radioactive sources disposal
(SHARS)
Naturally occurring Low volume Residues of processed water <5.2Bq/g Near-surface disposal (e.g., shallow
radioactive materials trench)
(NORM) Bulk Oil and gas drilling, phosphate >5.2Bq/g Near-surface disposal (e.g., shallow
production (classified as radioactive trench or engineered)
waste)
751
• Establishment of methods and approaches for building trust among persons

involved and affected by the management of radioactive waste
• Implementation of radioactive waste management methods that ensure the pro-
tection of people and the environment both now and in the future
• Implementation of physical protection systems relevant to radioactive waste
• Incorporation of nuclear safeguards requirements in the design and operation of
facilities for the management of spent nuclear fuel
• Development of solutions that provide for the long-term management of radio-
active materials and waste
• Promotion of radioactive waste management methods and schemes that save
resources and utilize them efficiently
• Steady improvement of methods and technologies in radioactive waste management
Furthermore, while managing radioactive waste, the principle of interdependence

should be respected requiring preventing any actions that may preclude further waste
management steps.
International Obligations
The Kingdom of Morocco has committed to the following legally binding and
nonbinding international agreements:
Legally Binding Agreements

• Convention on the Physical Protection of Nuclear Material (CPPNM) (entered in
force in 2002)
• Amendment to the Convention on the Physical Protection of Nuclear Material
• Convention on Early Notification of a Nuclear Accident (entered in force
in 1993)
• Vienna Convention on Assistance in the Case of a Nuclear Accident or Radio-
logical Emergency (entered in force in 1993)
• Convention on Nuclear Safety (signed in 1994)
• Joint Convention on the Safety of Spent Fuel Management and on the Safety of
Radioactive Waste Management (ratified in 2001)
• Vienna Convention on Civil Liability for Nuclear Damage (signed in 1984)
• Protocol to Amend the Vienna Convention on Civil Liability for Nuclear Damage
• Convention on Supplementary Compensation for Nuclear Damage
• Joint Protocol Relating to the Application of the Vienna Convention and the Paris
Convention
• Basel Convention on Control of Transboundary Movements of Hazardous Wastes
and their Disposal
• Bamako Convention on the ban on the Import into Africa and the Control of
Transboundary Movement and Management of Hazardous Wastes within Africa
• London Convention on the Prevention of Marine Pollution by Dumping of Waste
and Other Matters
Nonbinding Agreements
• Code of Conduct on the Safety and Security of Radioactive Sources
• Supplementary Guidance on the Import and Export of Radioactive Sources
• Code of Conduct on the Safety of Research Reactors
Purpose of National Radioactive Waste Management Policy

and Scope
Policy Objectives
Safety and Security Objectives

The safety and security objectives for the management of spent nuclear fuel and
radioactive waste in Morocco are stated as follows in Article 85 of Law N 42-142
on Nuclear and Radiological Safety and Security under development:
• To achieve and maintain a high level of safety and security regarding the
management of spent nuclear fuel, radioactive waste, and other radioactive
materials such as NORM
• To ensure adequate protection of workers, the general public and the environ-
ment, now and in the future, from the harmful effects of ionizing radiations,
without compromising their ability to meet their expectations
• To prevent accidents and to mitigate their consequences
Management of radioactive waste in Morocco follows the Fundamental Safety

Principles of International Atomic Energy Agency and respects international treaties
and conventions to which the country is a signatory, in particular the Joint Conven-
tion on the Safety of Spent Nuclear Fuel and the Convention on the Physical
Protection of Nuclear Material.
Responsibility for RWM

Until such time as they are accepted for centralized storage and disposal by the
authorized National Radioactive Waste Management Organization (WMO), the
primary responsibility for safety and security of radioactive waste and disused sealed
radioactive sources (DSRS) rests with the owners and the operators of the facilities
where the wastes are generated and managed and with the owners of sealed radio-
active sources. However, responsibility for ensuring the long-term safety of radio-
active waste management rests with the State, which is also responsible for
managing legacy waste and orphan disused sealed radioactive sources, and radioac-
tive residues from some past facilities and activities. The State responsibilities are
implemented through appointed organizations and institutions acting on behalf of
the Government.
National Security Infrastructure

The Government establishes conditions for creating a national security system
ensuring physical protection of all radioactive waste and facilities where such
material is placed. The security system includes also measures preventing
unauthorized creation or import of radioactive waste or their recovery once it has
been created, either as it has been abandoned, lost, misplaced, stolen or transported
without proper authorization.
Long-Term Management of RW
For radioactive wastes and disused sealed radioactive sources that will remain
hazardous for many years, the Government recognizes two long-term management
options. The first, which is preferred, entails repatriation to the country of origin.
This option will be applied, when practicable, to disused sealed radioactive sources
and research reactor fuel. The second option is temporary storage followed by final
disposal in a suitably designed disposal facility. The nature of this disposal and its
timing will be decided by Government in due course having due regard to
intergenerational equity, i.e., the principle that present-day society has an obligation
to deal with the liabilities it creates rather than pass them on to future generations.
Implementation of disposal will be performed by CNESTEN.
Management of Register of Sources and National Inventory

of Radioactive Materials and Waste
The NRSSA will maintain a register of the nature, location, and properties of all
radioactive sources currently held by licensees; with the assistance of the
CNESTEN, it will also develop and maintain an inventory of current and prospective
radioactive waste and materials and disused sealed radioactive sources describing
their location and their physical, chemical, and radiological properties.
National Obligations and Priorities
Liabilities for RWM

The license holders of installations generating radioactive waste including disused
sealed radioactive sources or naturally occurring radioactive materials (NORM)
shall be responsible for the safe management of such wastes or materials as long
as ownership has not been transferred to and accepted by another lawfully licensed
entity. The administrative, technical, and financial arrangements for the management
of such wastes or materials shall comply with the requirements of the Regulatory
Framework described by the National Policy for RWM and shall be consistent with
the provisions of the National Strategy for RWM.
Waste Minimization
The generation of radioactive waste shall be kept to the minimum practicable. In this
regard, users of radioactive materials shall prioritize the reuse and recycling of
materials. Exemption and clearance criteria shall be issued by the Nuclear and
Radiological Safety and Security Agency (NRSSA).
Import/Export of RW
The import and export of RW is prohibited (in compliance with Article 5 of Law N
42-142 under development). Authorization for temporary export of RW for pro-
cessing abroad and re-importation of resulting radioactive residues may be excep-
tionally granted by the NRSSA (in compliance with Article 36 of Law N 42–142).
Repatriation of DSRS
Priority shall be given by owners to returning their disused sealed radioactive
sources to the respective supplier countries or to another country for recycling or
reuse.
Management of Spent Nuclear Fuel

The entity responsible for the management of nuclear fuel from the research reactor
shall give priority to returning all spent nuclear fuel to the supplier country.
Disposal as Final End-Point for Radioactive Waste Management

It is accepted that, for those solid radioactive wastes that are not repatriated or decay
stored to exemption levels, long-term safety and security may only be achieved by
disposal in a suitably authorized facility. This recognizes uncertainty over the long-
term future and the obligation to avoid passing on liabilities created by the current
generation to future generations.
Liquid and gaseous wastes may be discharged to the environment provided that
the Regulatory Authorities are satisfied that this can be done without harm to
workers, the public, or the environment.
General Principles of the Morocco Policy for Radioactive Waste

Management
The general principles of the Morocco policy for radioactive waste management
illustrated below conform to international standards adopted by the International
Atomic Energy Agency (IAEA) and Morocco’s sustainable development goals.
Therefore, in accordance with these goals and international safety objectives, this
policy supports the safe management of radioactive waste in order to protect present
and future generations in line with the following principles:
• Protection of Human Health: Radioactive waste shall be managed in such a way

as to secure an acceptable level of protection for human health.
• Protection of the environment: Radioactive waste shall be managed in such a
way as to provide an acceptable level of protection of the environment, including
natural resources.
• Protection beyond national borders: Radioactive waste shall be managed in

such a way as to assure that the possible effects on human health and the
environment beyond national borders will be taken into account.
• Protection of future generations: Radioactive waste shall be managed in such a
way that predicted impacts on the health of future generations will be within
relevant levels of impact that are acceptable today.
• Burdens on future generations: Radioactive waste shall be managed in such a
way that will not impose undue burdens on future generations.
• National legal framework: Radioactive waste shall be managed within an
appropriate national legal framework, including clear allocation of responsibili-
ties and the provision for effectively independent regulatory functions.
• Control of radioactive waste generation: Generation of radioactive waste shall
be kept to the minimum practicable.
• Safety of facilities: The safety of facilities for radioactive waste management
shall be appropriately assured and regulated throughout its lifetime.
• Responsibility of waste generator: The waste generator shall be responsible for
the financial obligations associated with the safe management and disposal,
including regulatory oversight, of the generated waste.
• Transparency in waste management: All radioactive waste management activ-
ities shall be conducted transparently. Information that does not compromise the
security of the radioactive materials shall be shared with the public and other
relevant stakeholders.
• Decision-making: The decision-making process shall be based upon scientific
information, risk analysis, and recommendations from competent national and
international institutions dealing with radioactive waste management.
• Precautionary principle: A conservative approach shall be adopted in the event
of uncertainties regarding radioactive waste management.
• Importing and exporting radioactive waste: It shall not be permitted to import
or export radioactive waste, in all its forms, to or from Morocco, under any
circumstances.
• National cooperation: Due to the nature of activities related to radioactive waste
management, cooperation and coordination between the various stakeholder
institutions shall be based upon clear mechanisms to prevent duplication of efforts
and maximize the efficiency.
• International cooperation: Radioactive waste management may require coop-
eration with other countries and shall be done so in accordance with the frame-
works of bilateral, regional, and international agreements.
• Capacity building: Adequate opportunities shall be provided to build capabili-
ties and develop skills on a national level related to radioactive waste
management.
The principles listed above guide application of this policy by the establishments,
institutions, individuals, and facilities engaged in business related to, and resulting in
the production, management, and disposal of, radioactive waste in any form and
from any process.
Organizational Framework and Allocation of Responsibilities
According to existing legislation, two regulatory authorities are currently involved in

authorizing and controlling facilities and practices related to RW and radiation
sources management. The licensing and regulatory control of nuclear installations
is assigned to the Ministry of Energy, Mines, Water, and Environment (MEMEE),
while the Centre National de Radioprotection (CNRP) has the responsibility, dele-
gated by the Ministry of Health (MoH), for the main regulatory functions of all other
radiation practices and sources. Both authorities perform regulatory functions; only
CNRP provides radiation protection services. Both Ministries are also in charge of
the development, promotion, or utilization of the same radiation practices that they
are meant to regulate.
Currently, there is no effectively independent regulatory authority adequately
empowered by legislation. The present situation is due to change with the
promulgation of a new Law on “Nuclear and Radiological Safety and Security”
and the subsequent establishment of a single and effectively independent
regulatory body.
Waste operators include license holders of facilities generating radioactive waste
mostly from nuclear applications (research, medicine, industry) and practitioners
licensed to utilize radiation sources and also responsible for the management of their
sources once they become disused.
The operation of the centralized system for radioactive waste management in the
Kingdom of Morocco relies upon the Centre National de l’Energie, des Sciences et des
Techniques Nucléaires (CNESTEN) established under the Ministry of Energy, Mines,
Water, and Environment (MEMEE)’s authority. CNESTEN is the waste management
organization responsible for the collection, transport, processing, and storage of all
radioactive waste, spent nuclear fuel, and DSRS generated in the country.
National Council for Nuclear Energy
The National Council for Nuclear Energy (Conseil National de l’Énergie Nucléaire –
CNEN) was established by Decree N 2-90-352 of 5 May 1993 under the Prime
Minister’s authority. CNEN is assigned, among others, the following missions:
• To propose orientations and objectives for the National Policy in the field of
peaceful uses of nuclear energy, and to propose implementation measures in this
respect;
• To advise on all issues related to nuclear regulations.
In the context of the National Radioactive Waste Management, the CNEN has a
role to play on behalf of the Head of Government’s Office and responsible Govern-
ment Ministries regarding the approval of the National Radioactive Waste Manage-
ment Strategy and its implementation. CNEN’s role is specified in section
“Radioactive Waste.”
Establishing a New Unified and Independent Regulatory Body
Under new Law N 142-12 on “Nuclear and Radiological Safety and Security,” a new
unified and independent regulatory body, so-called Nuclear and Radiological Safety
and Security Agency (NRSSA) will be established. The new Agency will take over the
regulatory functions currently assigned respectively to the Ministry of Energy and
Mines for the licensing and regulatory control of nuclear installations and to the CNRP
under the Ministry of Health’s authority for all other radiation practices and sources.
The new NRSSA will establish and issue regulations and guidance relating to the use
of radioactive substances and, in the context of this specific policy, for radioactive
waste management (including transport, storage and disposal). Specifically, it will set
standards for the safe storage and disposal of radioactive waste and prescribe a
stepwise approach to the implementation of radioactive waste disposal. It will monitor
the import and export of scrap metal with the aim of intercepting orphan sources and
contaminated material. It will control the import and export of radioactive materials,
maintain a register of radioactive sources held at licensees’ premises and an inventory
of radioactive waste and disused sealed radioactive sources. It will support Govern-
ment in the framing of new legislation and report to the Head of Government’s Office.
It will work closely with IAEA and will seek formal collaboration agreements with
similar regulatory authorities in other countries of the region.
Defining Role of Operators and Organization Responsible

for Centralized and Long-Term Radioactive Waste Management
Waste Generators and Source Users:

License holders of facilities generating radioactive waste and practitioners licensed
to utilize radiation sources are required to perform their activities in compliance with
the objectives, principles, and requirements stated in the National RWM Policy.
Waste generators and source users bear primary responsibility for the safety and
security of their facilities and practices. In this respect, Article 85 of new Law N
142-12 requires the waste generators to take appropriate steps to manage their waste
according to the following requirements:
• To ensure that the generation of radioactive waste is kept to the minimum practicable
• To take into account interdependencies among the different steps in radioactive
waste management, such as treatment, conditioning, storage and disposal
• To take into account the biological, chemical, and other hazards that may be
associated with radioactive waste management
• To apply the regulatory procedures for waste characterization and to manage the
waste
• To maintain updated records of their RW generated and/or managed (types,
characteristics, quantities, status, location) and to periodically report on those
waste to the NRSSA
• To periodically report to the regulatory body on the internal inventory and status
of radiation sources, including DSRS
Furthermore, the license holders of facilities generating radioactive waste are

required to periodically reassess the safety of their facilities and practices and
reevaluate their radiological and environmental impact on the workers, the public,
and the environment.
Waste Management Organization:

The Centre National de l’Énergie, des Sciences et Techniques Nucléaires
(CNESTEN) established under the Ministry of Energy and Mines (MEM)’s authority
is the national research and operational organization involved in nuclear activities,
including RW, DSRS, and nuclear fuel management. CNESTEN is assigned the
following missions relating to RW and SNF management:
• To site, develop, and operate RW/DSRS management facilities, nuclear research

laboratories, and a nuclear research reactor, all of them located at La Maâmora
Nuclear Research Centre
• To import and manage nuclear fuel
• To propose, in consultation with the relevant organizations, all technical and
regulatory measures to ensure adequate protection to man and his environment
• To collect, process, and store radioactive waste including disused sealed radio-
active sources.
Generating also RW from research and operational activities, CNESTEN has the
same obligations as any other waste generator.
Furthermore, as license holder of the waste management center established at La
Maâmora Nuclear Research Centre, CNESTEN is required to periodically reassess
the safety of their radiological and environmental facilities and practices and
reevaluate their impact on the workers, the public, and the environment.
Once radioactive waste and/or DSRS are collected by CNESTEN, the ownership
is transferred from the waste generators or source users to CNESTEN which takes
over all liabilities associated with the long-term management of RW and/or DSRS.
In the context of the National Policy, CNESTEN will also be responsible for the
development, construction, and operation of a national radioactive waste disposal facility.
In collaboration with relevant Government ministries, CNESTEN will have the
responsibility for developing and proposing the national strategy for radioactive
waste management. CNESTEN will continue to report to the Ministry of Energy and
Mines and will seek to collaborate with similar radioactive waste management
organizations in other countries of the region.
Updating and Strengthening the Policy

The new Nuclear and Radiological Safety and Security Agency (NRSSA) is established
under the new legislation, is assigned by the responsible Ministries the role of support
organization regarding the enactment, updating and strengthening of the Policy.
In this respect, NRSSA is responsible the following tasks:
• To advise Government Ministries on legal and regulatory aspects in relation to

nuclear and radiological safety and security;
• To propose new legislation and regulations to strengthen the Policy;

• To arrange for general public information on RWM issues;
• To promote a safety and security culture in the country among those involved in
nuclear activities.
National Strategy for Radioactive Waste Management
The purpose of the National Radioactive Waste Management Strategy is twofold:
• First, to define the means for achieving the goals and requirements set out in the
National Policy for the safe and secure management of spent nuclear fuel and
radioactive waste in the Kingdom of Morocco; and,
• Secondly, to develop and implement a coherent, integrated, optimized, and
sustainable management system encompassing all radioactive wastes types gen-
erated in the Country.
The National Radioactive Waste Management Strategy shall provide for cradle-
to-grave management of the following radioactive waste types:
• Radioactive waste from nuclear applications, including the operation of the

research reactor
• Radiologically contaminated materials from the scrap industry
• Disused sealed radioactive sources
• Spent nuclear fuel, when spent fuel is considered as waste
The National Strategy for the management of radioactive materials and waste and
spent nuclear fuel is elaborated under the responsibility of the main operator
CNESTEN in consultation with all the organizations involved in RWM activities,
i.e., generators of RW, NORM, owners/users of radioactive source. The scope of the
proposed strategy is wider than Morocco National Report to the IAEA Joint Con-
vention Review Meetings which does not include NORM.
The draft Strategy will be thoroughly examined by the NRSSA to verify its
compliance with the Country’s policy objectives and regulations applicable to
RWM and NORM management.
Disused Sealed Radioactive Sources
CNESTEN is responsible for collecting all DSRS, transporting and storing them
at the CNEM storage facility unless DSRS can be returned to the suppliers. In the
case of high-activity DSRS, priority is given to repatriating them to the country of
origin. Another management option for very short-lived DSRS is to keep them at
the users’ premises and to release them under regulatory control after appropriate
decay storage.
Unless DSRS can be managed through decay storage and then released in the
public under regulatory control, DSRS shall be transferred to an interim storage
facility waiting for a disposal solution to be available.
Depending on their radionuclide contents and activity, short-lived DSRS will
be safely disposed of in near surface engineered facilities, while, based on safety
considerations, long-lived DSRS will require to be disposed of deeper undergro-
und in appropriate structures such as the Borehole Disposal System designed by
the IAEA.
Only low and intermediate level radioactive wastes (LILW), short lived and very
short lived, are generated in Morocco. They originate from civilian programs for
nuclear applications in medicine, industry, and research.
Presently, Morocco does not generate any high level waste nor long lived
radiologically contaminated wastes.
Waste with very low activity concentrations, which fall below regulatory concern
or within discharge limits, are released to the atmosphere, sewer, or landfill. More
active but still very short lived radioactive waste are stored for decay and then
released or disposed as nonradioactive materials.
The RWM infrastructure in place takes care of all LILW generated in Morocco
and covers all the management steps from generation to storage through transpor-
tation and processing. Radioactive wastes collected by CNESTEN at the genera-
tors’ sites are transported to La Maâmora CENM to be processed and then stored.
Aqueous radioactive effluents are treated by evaporation while solid wastes are
segregated into compactable and noncompactable waste. An in-drum compactor is
used for compactable waste placed in 100-l drums. Organic wastes are solidified
and conditioned in 100-l drums. Cement mortar mix is used as immobilization
matrix.
The scrap metal industry and the main harbors are equipped with fixed portal
radiation monitoring systems to detect the presence of contaminated metals or
radioactive sources in shipments. The staff is trained by the CNRP and any suspi-
cious radioactive material detected is taken care of by CNRP and eventually
transferred to CNESTEN.
The waste classification enforced by Morocco which is consistent with the IAEA
RW classification specifies suitable disposal modes from a safety standpoint as final
end points for each class of radioactive waste generated in the country. According to
their radiological characteristics, RW currently generated in the country which
cannot be stored for decay and then cleared under regulatory control, require
disposal in dedicated facilities. RW are mostly short lived (i.e., half-life below or
equal to 30 years and long-lived radio-emitters in limited quantity) and belong to
either the Very low level waste class (VLLW) or the Low level waste class (LLW).
According to international safety standards and good practices, VLLW is suitable for
disposal in near surface landfill type facilities while LLW can be accommodated in
engineered near surface disposal facilities.
Strategic National Framework for Radioactive Waste

Management
The strategic national framework for radioactive waste management in Morocco

applies the following basic principles:
• It is regarded as essential by formulation of recommendations to the relevant

decision-makers to legitimize a decision to proceed with a particular primary
course of action (e.g., deep geological disposal or borehole disposal) on the basis
of the principle of reasonable consensus.
• Final disposal is regarded as the ultimate step in the radioactive waste manage-
ment process, although a step-wise waste management approach is acceptable.
Long-term storage of certain types of wastes (e.g., HLW, LLW, and DSRS) may
be regarded as one of the steps in the management process.
• Achieving the highest degree of passive safety and security in management and
disposal of radioactive waste.
• Construction, operation, decommissioning and closure of waste generating, manage-
ment, and disposal facilities in accordance with all applicable regulatory requirements.
• The following hierarchy of waste management options shall be followed where
practicable.
– Waste Avoidance and Minimization
– Re-use, processing, and Recycling
– Storage
– Conditioning and Disposal
• The national strategy for radioactive waste management shall cover the complete
life cycle of radioactive waste management from the phase of generation through
to the final disposal phase.
• Although a degree of institutional control in some facilities may be required for an
indefinite period, the relevant regulatory body must specify the period for which
active institutional control may be assumed for the purposes of safety assessments.
• In the event that retrieval of radioactive waste is required, measures aimed at
enhancing retrievability should not compromise the operational and long-term
safety of a disposal option.
• The transfer of waste among generators shall be considered, provided all issues
pertaining to ownership and liability and safety are addressed.
• To minimize the burden on future generations, decommissioning and closure of
facilities should be implemented as soon as practicable.
• The deliberate dilution of radioactive waste is not acceptable unless justified in
the form of a safety case and approved by an appropriate regulatory authority.
Monitoring Strategy Implementation
The National Council for Nuclear Energy (Conseil National de l’Energie Nucléaire –
CNEN) will be responsible for monitoring the implementation of RWM infrastruc-
ture development in Morocco and reporting on the progress of implementation or
any shortcomings to the responsible Ministries. The CNEN will identify any devi-
ation from the approved Plan, will assess the potential consequences, will analyze
the reasons for any major difficulty or issue, whether political, administrative,
technical, or financial, and will propose remedial actions.
Performance indicators are used to conclusively measure progress towards the
targets set (e.g., milestones) and compliance with operational goals. They take
into account elements critical to the successful implementation of the National
Master Plan as well as individual waste management steps. Performance indica-
tors cover safety, environmental and financial aspects of implementation, as well
as the timely achievement and be verifiable both in a quantitative as well as
qualitative manner.
Updating the Strategy
The National Strategy for RWM will be updated every 3 years by the responsible
organizations on the basis of the revised inventory of Radioactive Waste and in
conjunction with the preparation of Morocco National Report to the IAEA Joint
Convention review meeting.
National Model for Radioactive Waste Management
The national model for radioactive waste management indicates the waste manage-
ment processes from waste generation through to the main waste management
end-points and institutional controls. Although not all steps may apply to all waste
streams/categories, the following management steps should be considered.
Waste Generation
Radioactive waste, spent nuclear fuel, and materials that are potential radioactive
waste are continuously generated during the execution of regulated activities.
Radioactive waste may also exist due to previous activities and/or historic pro-
cessing of radioactive materials (legacies).
Predisposal Management of Radioactive Waste
Predisposal management of radioactive waste is required to ensure:
• Waste prevention and waste minimization.

• The selection of suitable waste management options.
• A waste package that meets acceptance criteria for disposal, storage, and for any
associated handling and transportation activities.
• Waste or material that is suitable for authorized disposal/discharge, authorized

re-use/recycling, and clearance from regulatory control.
During the generation of radioactive waste, the emphasis shall be on the

control of waste generation and minimization (so as to minimize processing
costs, risk to workers, and the potential for environmental impacts). The unavoid-
able radioactive waste shall be classified to enable category-specific waste
management.
The options for management and disposal of each waste category shall be
evaluated in a systematic way (such as a multi-attribute analysis). The outcome of
the multi-attribute analysis is regarded as the best available technology not entailing
excessive cost (BATNEEC).
The extent of the waste processing shall depend upon the waste acceptance
criteria for regulated disposal and the anticipated acceptance criteria and storage
period in the case of regulated storage. Category-specific waste processing, namely,
pre-treatment, treatment, and conditioning shall be performed to obtain waste pack-
ages that are suitable for storage and/or disposal.
Waste shall be characterized throughout the predisposal management steps. Waste
category-specific characterization requirements shall be specified and shall cover the
establishment of physical, chemical, biological, and radiological properties to deter-
mine waste processing needs and the ultimate suitability of a waste package for
storage and disposal. Waste characterization data and records shall be used for
verification and quality assurance purposes.
Transportation of waste may be required between the various predisposal man-
agement steps and may include on- and off-site transportation.
Storage of radioactive waste is an important step of the radioactive waste man-
agement process. There may be a need for storage, for instance, for decay of
radionuclides with short half-lives, for heat dissipation, providing for an opportunity
for radioactive waste to be processed efficiently (if the necessary equipment or
technologies are not available), or in the interim prior to identification and estab-
lishment of suitable facilities for final disposal. Stored radioactive waste should be
retrievable, easily monitored, and kept in a state in accordance with relevant safety
requirements of safety. In the case of regulated disposal, waste packages shall be
stored temporarily and transported to a waste repository. In the case of regulated
storage, waste and/or waste packages shall be stored for an authorized period for
future processing and/or disposal.
Waste Management End Points
The main waste management endpoints correspond with the waste management
options and may be regarded as the outcome of a specific waste management
option. Regulated disposal requires continued regulation of the disposal site for a
predetermined duration, thereafter the site will be placed under institutional
control.
Long-Term Waste Management
There are two long-term waste management options envisioned in Morocco at present:
• Above ground long-term storage in engineered facilities for the bulk of the
mining, milling, and decommissioning waste.
• Near-surface disposal for LILW at building of storage in the radioactive waste
management unit of CNESTEN/CENM
• Trench-type disposal of NORM waste and VLLW from decommissioning.
• Borehole disposal (according to the Borehole Disposal System; BDS) of DSRS.
Disposal presents the most challenges and it is an area where coordination is of

utmost importance.
The building of storage in the radioactive waste management unit of
CNESTEN/CENM near-surface facility shall continue to be used as a national
disposal site for LILW until capacity is reached. The disposal shall be conducted
within the nuclear authorization framework of the appropriate nuclear regulatory
authorities.
The Government shall initiate investigations into the best long-term option (e.g.,
large-diameter boreholes or deep geological disposal) for the management of radio-
active waste, which does not comply with the waste acceptance criteria of the
building of storage near-surface facility (i.e., HLW and waste containing long-
lived radionuclides). The process of selecting a site for long-term waste management
shall involve a comprehensive public participation process.
Management of Disused Sealed Radioactive Sources
DSRS are broadly used in agriculture, medicine, industry, including for

non-destructive testing, radioactive sterilization, manufacturing of health care prod-
ucts, control systems in production line operations, raw material elemental analysis,
evaluation of mineral resources, food irradiation, smoke detection, and medicine
such as for treatment of malignant tumors. Upon removal from use, DSRS need to be
managed in a safe manner.
If the activity and physical condition of the DSRS allows for further use, transfer
of ownership to another user may offer economic and environmental benefits. In the
case of termination or transfer of a DSRS license, the regulatory authority shall be
responsible entity for issuing new licenses.
According to national regulations, all DSRS imported be returned to the manu-
facturer. In the event that this is not possible, then the regulatory authority shall
classify the DSRS as radioactive waste, order its disposal, and issue appropriate
licenses for transfer of ownership to the national nuclear operator.
DSRS may be stored (in a centralized facility) prior to disposal, especially for
DSRS containing short-lived radionuclides, in the event that they meet the waste
acceptance criteria for the destination facility. This facility allows for potential
Fig. 4 Disused sealed radioactive sources
retrieval of the source for recycling/reuse, as permitted by the appropriate regulatory

authority.
Options for disposal of DSRS may vary according to the radionuclides and
activities of the DSRS. DSRS may be disposed of in engineered near-surface
disposal facilities provided that they meet the waste acceptance criteria of the facility.
Geological disposal offers the highest level of safety and security, and the feasibility
of appropriate options (e.g., BDS) shall be investigated to this end (Fig. 4).
Management of Spent Radioactive Ion Exchange Resins
Ion exchange resins are employed extensively in the nuclear industry to remove the
radioactive contaminants such as neutron activation products and fission products
which may have leaked from fuel elements. The spent radioactive ion exchange
resins have been produced during the operation of the nuclear facilitieds in
the nuclear industry. The resins loaded with radioactive nuclides could not be
regenerated and reused. These waste resins should be properly treated and disposed
in order to minimize their potential hazard to the environments. The choice of
treatment options for spent ion exchange resins must take into account their phys-
icochemical and radiological characteristics. Basically, there are two main methods
for the treatment of this type of radioactive waste: (1) destruction of organic
compounds to produce an inorganic intermediate that can be packaged and/or stored,
and (2) direct immobilization in different matrices. The destructive methods for the
treatment of spent ion exchange resins such as pyrolysis (Matsuda et al. 1986),
incineration (Long 1990; Johnson and Fong 1978; Ziegler et al. 1977; Hercigonja
et al. 2012; Valkiainen and Nykyri 1982), catalytic extraction. . . are intended to
modify the physicochemical and radiological characteristics of waste by preparing it
for final disposal. The immobilization consists in solidifying the waste by incorpo-
rating it into a matrix of storage and/or final disposal. The immobilization matrices
used for ion exchange resins are cement, bitumen, glass.
Compared to other immobilization matrices, cementing has the advantage of a
simple, less costly implementation, the final cemented waste is incombustible and
has good stability with respect to ionizing radiation for low-level waste and medium
activity. To this end, cementation is the most widely used process in several
countries, including Morocco.
National Process for Implementing the Radioactive Waste

Management Strategy
Radioactive waste stream-/category-specific waste management plans per site/indus-

try shall be based upon an evaluation process and authorization as described in this
document.
The elements for the process are:
• Identification and nature of site-specific radioactive waste stream/categories and

associated waste management issues.
• Consideration and listing of realistic options for the long-term management of
specific radioactive waste management streams/categories.
• Systematic evaluation of the merits and disadvantages of each option (e.g., in the
form of a multi-attribute analysis covering cost-effectiveness, technological sta-
tus, operational safety, social and environmental factors).
• Identification of the best available technology not entailing excessive cost
(BATNEEC).
• Acceptance of BATNEEC as waste stream-/category-specific strategy.
• Review mechanisms of industry-/site-specific waste management plans.
Site-/industry-specific radioactive waste management plans (action plans) shall

be developed in accordance with the process described in this document and
submitted to an appropriate regulatory authority for acceptance and approval or
comment, as appropriate.
The framework for the development of site-/industry-specific radioactive waste

management plans includes the following:
• The development and submission of plans shall be scheduled with the appropriate
regulatory authority. Separate plans and proposals may be submitted for specific
waste streams/categories and scheduled according to the anticipated time required
for the development of plans.
• Plans shall cover all waste streams/categories on a site or in a specific industry.
• Plans shall identify all waste management options as well as the applicable pre-
disposal management steps required for a specific option, and the details thereof
including volume estimates (preferably conservative).
• The merits and disadvantages of each of the listed options shall be evaluated in a
balanced and systematic way (e.g., using a multi-attribute analysis approach).
The methodology for evaluation and selection of an option (BATNEEC) shall be
described and justified per site/industry. This should be submitted to the appro-
priate regulatory authority prior to the submission of waste management plans for
concurrence on methodology. It should be noted that all regulatory requirements
must be met.
• Approved waste management plans shall be reviewed and re-submitted at a
frequency determined by the regulatory authority.
• The development process and associated considerations of the radioactive waste
management plan are defined in national regulations and guidance documents
established by appropriate regulatory authorities.
Radioactive waste management and disposal stations may be established region-

ally within Morocco, appropriate to the types of radioactive waste generated in the
respective regions, in order to minimize the safety and security risks associated with
long-distance transport. These stations shall be equipped with the necessary com-
ponents to ensure safe and secure management of radioactive waste.
Conclusion
Radioactive waste is generated in a number of different kinds of facilities and it may

arise in a wide range of concentrations of radionuclides and in a variety of physical
and chemical forms. These differences result in an equally wide variety of options
for the management of the waste. There are a variety of alternatives for processing
waste and for short-term or long-term storage prior to disposal.
Different types of waste may be grouped for operational waste management
purposes. For example, waste containing radionuclides with short half-lives may
be separated from waste containing radionuclides with longer half-lives, or com-
pressible waste may be separated from noncompressible waste. Nevertheless, apart
from waste containing only short-lived radionuclides, all other types of radioactive
waste need to be eventually disposed.
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Actinide Speciation in Environment
and Their Separation Using Functionalized 31
Nanomaterials and Nanocomposites
N. Priyadarshini, K. Benadict Rakesh, and P. Ilaiyaraja
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 773
Background: Hydrolysis of Metal Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 775
Hydrolysis of Actinides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 776
Plutonium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
Complexities in Plutonium Aqueous Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
Hydrolysis and Polymerization of Tetravalent Plutonium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
Parameters Influencing the Formation of Plutonium Polymers/Colloids . . . . . . . . . . . . . . . . . . . 779
Probing the Formation and Structure of Pu(IV) Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 781
Size and Morphology of Pu(IV) Colloid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
Hydrolysis and Solubility of Pu(IV) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 784
Methods Adopted to Remove Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 786
Extraction of Pu(IV) Polymer/Colloid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 786
Depolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 787
Proposed Methods for Depolymerizing Pu(IV) Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 787
Uranyl Nitrate Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 788
Hydrolysis of Th(IV) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 788
Probing the Formation and Structure of Th(IV) Hydrolyzed Species . . . . . . . . . . . . . . . . . . . . . . 789
Size and Morphology of Hydrolyzed Th(IV) Polymer/Colloid . . . . . . . . . . . . . . . . . . . . . . . . . . . . 789
Hydrolysis and Solubility of Th(IV) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 789
Stability of Th(IV) Hydrolyzed Colloids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 790
Uranyl Effect on Polymerization of Th(IV) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 790
Molecular Weight of Th(IV) Hydrolyzed Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 791
Uranium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 791
Hydrolysis and Polymerization of Uranium(IV) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 791
Probing the Formation and Structure of U(IV) Hydroxide/Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . 792
Size and Morphology of U(IV) Colloid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 792
N. Priyadarshini
Department of Chemistry, SSN College of Engineering, Kalavakkam, Tamil Nadu, India
e-mail: priyadarshinin@ssn.edu.in
K. Benadict Rakesh · P. Ilaiyaraja (*)
Department of Physics, Indian Institute of Technology Madras, Chennai, Tamil Nadu, India

https://doi.org/10.1007/978-3-319-73645-7_143
772 N. Priyadarshini et al.
Hydrolysis and Solubility of U(IV) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 792

Molecular Weight of Hydrolyzed U(IV) Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 792
Hydrolysis of Uranium(VI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 793
Nanomaterials for Separation of Actinides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 794
Carbon Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 795
Carbon Nanotubes (CNTs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 795
Ligand-Impregnated MWCNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 798
Graphene Oxide (GO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 798
Magnetic Nanoparticles for Sorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 799
Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 800
Magnetic Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802
Mesoporous Materials for Sorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 803
Mesoporous Membrane for Sorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 804
Reverse Osmosis (RO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 804
Nanofiltration (NF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 805
Ultrafiltration (UF) Combined with Sorption/Precipitation/Complexation . . . . . . . . . . . . . . . . . . . . 805
Nanopolymer/Dendrimer-Assisted Ultrafiltration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 806
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 808
Abstract
Actinides are the major and most important environmental contaminants
associated with anthropogenic activities such as mining and milling of ura-
nium ores, and generation of nuclear energy resulting in the production of
nuclear reactor wastes. These actinides have greater migrating ability in
aquifer systems. But actinides in aqueous environment exhibit an inordinately
complex chemistry. As a result, the chemical interactions of actinides in the
environment are difficult to understand unless a detailed knowledge on their
chemical speciation, oxidation state, redox reactions, sorption characteristics,
temperature and pressure profiles, pH, and redox potential (Eh) is available.
The solubility and migration behavior are also related to these factors. To
predict how an actinide might spread through the environment and how fast
that transport might occur, we need to characterize all local conditions,
including the nature of site-specific minerals, and ligand concentrations. A
quantitative knowledge of the competing geochemical processes that affect the
actinide’s behavior is also mandatory. Once actinides enter the environment;
they pose major risk and hence safe management of radioactive waste with
minimum impact to environment gains major importance in addition to speci-
ation of actinides in environment. The major aim of radioactive waste man-
agement is to identify the chemical form of long-lived alpha-emitting
radionuclide species spread in the environment and to separate them. Func-
tional nonmaterial has gained wide attention and its increasing advancements
in multidisciplinary research will make it a good candidate for separation of
radionuclides. It is mainly because of their unique structure and exceptional
31 Actinide Speciation in Environment and Their Separation Using. . . 773
properties. In this chapter, we discuss in detail the basic research progress in

the speciation studies and separation of actinides in environment with the
emphasis on application of functionalized nanomaterials and nanocomposites
for the separation of radionuclides from the environment.
Keywords
Actinides · Nanomaterials · Speciation · Separation and radionuclides
Introduction
The actinides comprise 15 metallic elements with atomic numbers from 89 to

103, i.e., actinium through lawrencium. Among them actinium, thorium, protactin-
ium, and uranium exist naturally and the remaining so-called transuranium ele-
ments are produced by man through a variety of nuclear transformation processes
such as neutron irradiation, atom bombardment, and radioactive decay. The
amounts of the natural actinides on the earth are in the range of 3 1023 g for
thorium and 3 1022 g for uranium (Cornelis et al. 2005). Actinide series are
categorized into two groups, the light actinides (Th, Pa, U, Np, Pu, Am) and heavy
actinides (Cm, Bk, Cf, Es, Fm, Md, No, Lr). Usually light actinides are the main
environmental contaminants associated with anthropogenic activities such as min-
ing and milling of uranium ores, generation of nuclear energy, and storage of
nuclear waste resulting from the manufacturing and testing of nuclear weapons
(Nagasaki and Nakayama 2015). Increased global demand for electricity produc-
tion resulted in adopting nuclear technologies which further led to generation of
large quantities of radioactive waste. Moreover majority of the radioactive wastes
originate from nuclear reactors and the suitable way to be dealt with is by
reprocessing of spent nuclear fuel. But reprocessing of spent fuel faces a major
challenge due to hydrolysis of actinides that prevails in low-acid conditions leading
to many consequences and the important one being the criticality hazard due to
accumulation of plutonium metal. For radioactive materials stored in the ground or
in geological formations, the most probable transport medium is the aqueous phase
and several experimental evidences indicate that colloids and hydrolyzed species of
actinides can be the major factor in rapid migration of radioactivity in groundwater.
The low acidity of groundwater favors the formation of above-said species and thus
provides a potential transport pathway for migration of actinides and mainly
plutonium away from the repository (Cleveland 1967). That is the reason why the
radioactive waste is a serious environmental problem for which there is, as yet, no
universally accepted solution. Thus a comprehensive understanding of the complex
chemistry of actinides in aqueous media is required. There are two important factors
which need deep insights in order to avoid these consequences. Firstly speciation
studies have to be carried out. Secondly advance methods have to be identified for
the extraction of the actinide species prevailing in the environment. Most of the
speciation studies are carried out with actinides from thorium to curium and the
concentration range for speciation studies with actinides is mostly below
1 105 M (Rand et al. 2007). At high concentrations, the radioactivity of these
elements can cause radiolysis of actinide species in the environment. Actinides can
exist in variety of oxidation states and most commonly in trivalent and tetravalent
states. The element thorium exists only in the tetravalent oxidation state. In this
oxidation state, the solubility generally is very low and hydrolysis is the most
important reaction (Knope and Soderholm 2013b). The elements uranium, neptu-
nium, and plutonium show a wide variety of oxidation states. Pentavalent ions are
known from the elements protactinium to americium. In the pentavalent oxidation
state, oxo-cations are formed. Uranium, neptunium, and plutonium are stable in the
+6 oxidation state. A stable form of a heptavalent ion is known from neptunium, and
plutonium can also be oxidized to the octavalent oxidation state (Tananaev et al.
2007). Actinide ions in aqueous medium often are not in a state of thermodynamic
equilibrium and their solubility and migration behavior are related to the form in
which the nuclides are introduced into the aquatic system. The solubility, transport
properties, bioavailability, and toxicity of actinides are dependent on their specia-
tion, composition, oxidation state, molecular level structure, and nature of the phase
in which the contaminant element or molecule occurs. The most important reactions
of actinides in environment are hydrolysis and complexation with inorganic ligands
such as carbonate, sulfate, phosphate, chloride, and organic ligands as well as humic
substances (Henry et al. 1992).
For the extraction or removal of radioactive nuclides from the aqueous environ-
ment, a variety of technologies have been investigated. To mention a few solvent
extraction, precipitation, membrane filtration, sorption, electrodeposition, steam/
solar evaporation, and phytoremediation are appropriate methods (Weigel et al.
1997). Among these, sorption, precipitation, and membrane filtration technique
have been widely used because they are easily carried out, economical, and can be
applied on a large scale for practical applications. The selection of an appropriate
technology for radioactive waste processing depends mainly on the characteristics
of the radioactive waste, the scale of waste production, and the final form of the
waste (Nagasaki and Nakayama 2015). Advances in synthetics chemistry
such as invention of nanomaterials, nanostructured materials, and nanocomposite
are providing unprecedented opportunities to develop effective separation pro-
cesses for treatment of radioactive waste. Nanomaterials with their fascinating
physiochemical properties can be used to circumvent many limitations of bulk
material and thus represent a paradigm shift in our thinking. Nanomaterials differ
from bulk materials not only in size, but also in terms of physicochemical properties
that can be used to develop new technologies and improve the existing ones (Shi
et al. 2012).
This chapter is mainly contributed for the detailed discussion of speciation of
actinides in the aqueous systems which are considered as a most prevailing condition
of the environment. It also discusses the methods used to remove the actinide species
from the environment by using nanotechnology.
Background: Hydrolysis of Metal Ions
The chemical behavior of metallic element in aqueous solution is determined by

the nature of the ionic or molecular species that it forms. In the absence of
strongly complexing ligands and depending on the acidity of the solution the
simple cation of the element often reacts with water itself (hydrolyzes) to form
hydroxo complexes. This is due to the fact that in aqueous medium, the metal
cations Mz+ are solvated by dipolar water molecules giving rise to aquo ions [M
(OH2)n]z+. Charge transfer occurs through the M-OH2 σ bond. Electron density is
transferred from molecular orbital of coordinated water molecule to empty
orbitals of metal cation. This results in the weakening of O-H bond and finally
deprotonation takes place leading towards the formation of bonds with oxygen
and OH ligand (Henry et al. 1992). Hydroxide ions are always present in water
at concentrations varying from >1 to <1014 M as a result of small self-
dissociation constant of water. The resulting complexes may be cations, neutral
molecules, or anions. They may be mononuclear or polynuclear. That is, they
may contain one metal atom or several (Baes and Mesmer 1976). The ability of
hydrated metal ions to hydrolyze depends on the ionic potential (charge to size
ratio) of the metal. Small and highly charged metal ions are highly prone to
hydrolysis. The hydrolysis constant increases in the order M4+ > M6+ > M5
+
> M3+ mainly due to decrease in ionic radius and increase in Lewis acidity of
the metal ion (Altmaier et al. 2013). The initial step in the hydrolysis of a cation
is usually the formation of the mononuclear species MOH(z-1)+ and in general it is
represented as
Mzþ þ H2 O , MOHðz1Þþ þ Hþ (1)
Complete reaction is represented by including water of solvation:
þ ðz1Þ
MðOH2 Þzþ
n , MðOHÞðOH2 Þn1 þ H (2)
In the above reaction a proton is lost by a solvating water molecule and on further
hydrolysis,
ðz1Þ þ
MðOHÞðOH2 Þn1 ! MðOHÞ2 ðH2 OÞz2
n2 þ H (3)
ðz2Þ þ
MðOHÞðOH2 Þn2 ! MðOHÞ2 ðH2 OÞz3
n3 þ H (4)
and so on. But in reality complete hydrolysis does not happen; instead other
chemical reactions or aggregation of two or more hydrolyzed species takes place
and in general it is represented as follows.
(y-1)+ (y-1)+
OH H2 O
(H2O)d-2M M(H 2O)d-2
+
OH2 HO
ð5Þ
(y-1)2+
H
O
(H2O)d-2M M(H 2O)d-2 + 2H2O
O
H
When this reaction further continues, then there is a possibility of formation of

high-molecular-weight polynuclear chains. The determination of the identity and
stability of dissolved hydrolysis products has proven to be a difficult and challenging
task primarily for two reasons:
I. The hydroxide complexes formed are often polynuclear, that is, they contain
more than one metal ion. It will be readily perceived that this can result in the
formation of a greater variety of species during the hydrolysis of cations. More
hydrolysis products present simultaneously in appreciable amounts.
II. The range of pH over which the formation of soluble hydrolysis products can be
studied is often limited by the precipitation of the hydroxide or the oxide of the
metal cation (Baes and Mesmer 1981).
Hydrolysis of Actinides
Hydrolysis reactions are the primary complexation reactions of actinide elements in

aqueous solution. It is mainly correlated with the electrostatic interaction energy
between the actinide ion and the OH ligand (Choppin 1983; Grenthe and
Puigdomenech 1997; Neck et al. 2001). The general order is Pu4+ > Np4+ >
U4+ > Pa4+ > Th4+. The effective charge of the actinide ions decreases in the
order of An4+ > AnO22+ > An3+ > AnO2+. Due to high electric charge, tetravalent
actinides can hydrolyze even under very acidic conditions (pH < 3 depending on
actinide) (Walther et al. 2007). In the near-neutral pH, An(OH)(aq) species dominates
in the absence of other complexing ligands. Actinide ions in the trivalent and
tetravalent states in acidic solutions are in the form of the simple hydrated ions
An3+ and An4+, whereas An5+ and An6+ exist as trans-dioxo cations. This is due to
large positive charges which make them readily strip oxygen atoms from water
molecules. They are extremely stable and have a symmetric and nearly linear
structure [O = An = O]n+ where n = 1,2. This structure decreases the effective
charge on the central actinide ion making it less prone for hydrolysis compared to
tetravalent actinides (Choppin 1999).
Plutonium
Among the actinides, plutonium is the most chemically diverse and fascinating
element in the periodic table. Plutonium is generated by transmutation of uranium
in nuclear reactors in large scale. Plutonium has 18 isotopes. The most important
among these are 238Pu (t1/2 = 86 years) and 239Pu (t1/2 = 24,110 years) (Clark et al.
2006). The ground-state electronic configuration of atomic plutonium is [Ru]5f 67s2.
Plutonium ions in solution exist in +3, +4, +5, and +6 oxidation states as Pu3+, Pu4+,
PuO2+, and PuO22+ (Cleveland 1970). The chemistry of plutonium is in great
contrast to the light elements of periodic table and it is very difficult to control.
Some of the complexities of plutonium chemistry in aqueous medium are listed as
follows.
Complexities in Plutonium Aqueous Chemistry
Three reaction pathways have to be considered while investigating plutonium

in aqueous systems: hydrolysis, polymerization and colloid formation, and
redox reactions of different oxidation states of plutonium. It is difficult to study
one particular reaction without the interference of the other. Because all the
reaction takes place simultaneously, that is, mainly due to the same redox
potentials of the couples, Pu (III)/Pu (IV) (E0 = 1.031 V) and Pu (IV)/Pu
(V) (E0 = 0.936 V), an equilibrium of two or more oxidation state may occur
in solution. Differences in redox potentials for different oxidation states of pluto-
nium are given in Fig. 1.
In other words, plutonium acts both as oxidizing and reducing agent at the
same time. This is called disproportionation reaction. The disproportionation
reaction mainly happens at elevated temperature. The equations governing the
redox reactions for plutonium ions under acidic conditions are given as Eqs. 6, 7
and 8:
2Pu4þ þ 2H2 O , Pu3þ þ PuOþ

2 þ 4H
þ
(6)
Pu4þ þ PuOþ
2 , Pu
3þ
þ PuO2þ
2 (7)
2PuOþ þ
2 þ 4H , Pu
4þ
þ PuO2þ
2 þ 2H2 O (8)
0.94 V 1.04 V 1.01 V -2.00 V

Pu(VI) Pu(V) Pu(IV) Pu(III)
PuO2+ Pu3+ Pu(0)
PuO22+ Pu4+
0.99 V -1.25 V
Fig. 1 The redox potential differences for the plutonium aquo ions in 1 M perchloric acid, as well
as the potential difference between the plutonium aquo ions and pure Pu (Cleveland 1970)
• Conversely, under some conditions, two plutonium ions of different oxidation

states can react by means of a reproportionation reaction. The two ions are
simultaneously oxidized and reduced to form two ions of the same oxidation
state.
• Another important complexity is that all plutonium isotopes are radioactive. One
milligram of plutonium emits about 106 alpha particles per second, and the
radioactive decay is constantly adding energy to the plutonium solution. This
leads to radiolytic decomposition of water-producing redox reagents such as
short-lived radicals H, OH, and O. These radicals recombine to form H2, O2,
and H2O2. Thus radiolysis tends to reduce Pu(VI) and Pu(V) to Pu(IV) and Pu(III)
states (Clark 2000).
Hydrolysis and Polymerization of Tetravalent Plutonium
The tendency towards hydrolysis, polymerization, and further to colloid formation is

strongest for tetravalent plutonium as compared to other oxidation states due to its
high effective charge. The effective charges for different oxidation state of pluto-
nium are Pu4+(~ + 4) > PuO22+ (~ + 3.3) > Pu3+ (~ + 3) > PuO2+ (~ + 2.2). Pu(IV) is
stable only at very high acidities and considerable amounts of Pu(III), Pu(V), and Pu
(VI) are formed at pH > 0 as shown in Fig. 2 (Walther 2008).
Only at pH < 0.5, Pu4+(aq) is the dominant species whereas with increasing pH
the hydrolysis reaction leads to the quantitative formation of mononuclear com-
plexes Pu(OH)n 4n where n = 1–4. Rapid polymer formation takes place even in
1 103 and 1 104 M Pu(IV) solutions and close to solubility (Kumar and
Koganti 1997). The polymeric plutonium refers to a hydrolytic form which is
characterized by its bright emerald green color. The only means by which polymer
formation can be avoided is to detect colloids that are formed initially in the solution.
This is because the freshly formed polymer can be depolymerized where as aged
ones are difficult due to conversion of amorphous to crystalline form which involves
the modification of hydroxyl bridges to oxo bridges as shown in Eq. 9 (Seaborg and
Loveland 1990).
Fig. 2 Plutonium oxidation-

state distribution depending
on –log[H+] [21] (Walther
2008)
m+
H H
O O
- yH 2 O
xPu(OH)n 4-n Pu Pu Pu
O O
H H
Hydroxy bridged
- yH 2 O ð9Þ
m+
O O
- yH 2 O
Pu PuO 2
Pu Pu
O O
oxo bridged
Parameters Influencing the Formation of Plutonium

Polymers/Colloids
The formation and properties of polymers and colloidal hydroxides are directly
dependent on pH of the solution. At alkaline pH, some hydroxides can form anionic
complexes and possibly polymers. With increase in pH the degree of polymerization

and formation of colloidal aggregates also increases (Schuelein 1975). Ionic strength
of the electrolyte affects the solubility. Increase in ionic strength increases the
coagulation. Concentration of metal ion has direct effect on polymerization and
colloid formation. With decrease in Pu(IV) concentration, the pH of colloid forma-
tion increases (Bitea et al. 2003b). The rate of polymerization is a function of
temperature. Polymerization can occur even at room temperature in solution less
acidic than 0.3 M H+ and in 1.26 M H+ at boiling temperatures. The amount of
polymer formed at 75 C is ~3.5 times higher than the amount at 25 C when the
initial acidity is 0.075 M (Costanzo et al. 1973).
The free energy of plutonium polymer is estimated as about 341.9 kcalmol1
whose solubility product of Pu(OH)4 corresponding to this number is 2.5 1056
(Silver 1983). This shows that the polymerization phenomenon is a very rapid and
irreversible process (Toth et al. 1981). Under conditions of low acidity and elevated
temperature, the polymeric species require drastic treatment for conversion to the
ionic state. The presence of low concentrations of Pu in natural waters and in
disposal streams is of much interest to those concerned with reactor and radiation
safety. These solutions are usually nearly neutral and any plutonium is probably in
the polymeric state.
Formation of plutonium colloids can be detected by spectroscopic studies as each
oxidation state of plutonium and polynuclear plutonium has its own characteristic
color (Fig. 3a). The absorption spectrum of polymeric Pu(IV) state is different from
those of other plutonium species (Fig. 3b). At pH 0–2, there is a steady decrease in
the characteristic absorption band at 470 nm characteristic of ionic Pu(IV). They also
b 000
100
60
colloids Pu(VI)
absorptivity (M–1cm–1)
50
40 Pu(IV) Pu(III)
30
20
10 Pu(V)
0
400 500 600 700 800
wavelength (nm)
Fig. 3 (a) Characteristic colors of each oxidation state of Pu and Pu colloids (Clark 2000). (b)
Absorption spectra of different oxidation state of Pu and Pu colloids (Rabideau and Kline 1960)
show relatively broad, low-intensity bands and rather intense with increasing absorp-
tion below 460 nm (Rabideau and Kline 1960). Polymerization of Pu(IV) leads to
alterations in redox equilibria and additional easily identifiable spectral feature
around 620 nm appears for the presence of small Pu(IV) colloids. Absorption spectra
of aged polymers do not show any difference with that of fresh polymers except the
pronounced 620 nm peak (Cleveland 1967).
Probing the Formation and Structure of Pu(IV) Polymer
Though first step in the formation of polynuclear species is the condensation of

mononuclear species, there are no reports on the solution structure of Pu
(IV) mononuclear hydroxides. As an evidence for the presence of dimer, an X-ray
diffraction study has reported a solid-state structure of Pu2(OH)2(SO4)3.4H2O with
dimeric [Pu2(OH)2]6+ units linked by bridging sulfate ligands (Wester 1982). Electro-
spray ionization mass spectrometry (ESI-MS) studies on dimers, trimers, and tetra-
mers revealed the presence of mixed oxidation states of plutonium, i.e., Pu(III) and Pu
(V) (Walther et al. 2009). This gives an insight into the coexistence of monomeric and
pentavalent plutonium species with colloids and also their interference in redox
reactions (Newton et al. 1985; Rai and Swanson 1981; Neck et al. 2007). A hexa-
nuclear [Pu6(OH)4O4]12+ core with glycine ligands containing both oxo and hydroxo
bridges was also reported (Knope and Soderholm 2013a). The same linkage was also
found in case of lanthanides (Wang et al. 2000). The formation of the polynuclear
species is assumed to involve hydroxide or oxygen bridging of plutonium ions but
some reviews consider such species to be thermodynamically unstable (Lemire et al.
2001; Guillaumont et al. 2003). As an alternative they favor colloid formation from
mononuclear hydroxide complexes. Thus Pu(IV) colloids are more stable in contrast
to other tetravalent species such as Th(IV) and U(IV). The most widely accepted
mechanism of formation of plutonium colloid involves the condensation of [Pu
(OH)n](4n)+ through an olation reaction to yield hydroxo-bridged species. On further
condensation, the hydroxo-bridged oligomers produce mixed plutonium oxide
hydroxides (Knope and Soderholm 2013b). X-ray absorption fine structure (XAFS)
and laser-induced breakdown detection (LIBD) measurements proposed that the
formation of Pu(IV) colloids follows by stacking eightfold coordinated Pu units. It
involves the formation of a trinuclear species through hydrolysis and condensation of
a monomeric Pu(OH)2(H2O)62+ unit with a binuclear species to form single-edge
sharing, leading to the formation of neutrally charged species as product or a double-
edge sharing species with common corner. The dimers and trimers agglomerate and
eventually form nm-sized colloids (Fig. 4). The predominant species contain highly
asymmetric oxygen coordination which indicates the presence of different Pu-O bond
lengths from different coordinated oxygen atoms (–O, –OH, –OH2).
PuxOy(OH)4x2y(H2O)z (0 y 2x) has been proposed as colloid structure formed
by stacking of mononuclear or polynuclear building blocks on top of each other.
During this process, the cubic subunits are preserved and form a distorted fluorite
like plutonium lattice (Rothe et al. 2004). Single crystals of 38 plutonium
Fig. 4 Schematics showing mechanism of hydrolysis and polymerization of Pu4+(aq) leading to

formation of nm-size colloids Rothe et al. (2004)
nanoclusters [Li14(H2O)20[Pu38O56Cl54(H2O)8] and Li2[Pu38O56Cl42(H2O)]

15H2O] were isolated for structural characterization using single-crystal X-ray
diffraction. Both structures consist of the [Pu38O56]40+ core, wherein 38 8-coordinate
Pu(IV) cations are bridged exclusively via oxo linkages. The data clearly shows that
intracluster packing and structural topology of clusters of composition
[Pu38O56Cl54(H2O)8]40+ are identical with PuO2 and the surface is occupied by
chloride ion and water molecules (Soderholm et al. 2008; Wilson et al. 2011).
However the solid-state structure of the crystal does not contain Pu-OH moieties
which contradict the structure proposed by Rothe et al. (2004). Small-angle neutron
scattering (SANS) experiments were carried out on colloidal Pu(IV) suspensions in

aqueous phase and polymer extracted into C6D6 solutions by alkyl esters of phos-
phoric acid. The results revealed the presence of long, thin rodlike polymer in both
the phases. However the diameter of ellipsoids of extractant-Pu(IV) polymer com-
plexes in C6D6 is larger than that of aqueous polymer. This increase in diameter is
due to the attachment of extractant molecules around the rod-shaped Pu polymer.
The length of aqueous Pu(IV) polymer is larger than the polymer extracted in C6D6
(Thiyagarajan et al. 1990). A comparative study was also made between freshly
prepared and 5-year-old Pu(IV) colloids using Pu L3-edge extended X-ray absorp-
tion fine structure (EXAFS). The aged colloidal particles contain only 3–4 Pu atoms
with a structure very similar to solid Pu(IV) oxide but with shorter Pu-O and Pu-Pu
distances which was caused due to partial oxidation of Pu(IV) to Pu(V)/Pu
(VI) (Ekberg et al. 2013).
Size and Morphology of Pu(IV) Colloid
Polymeric plutonium was observed in two forms: amorphous and crystalline

primary particles and secondary particles which appeared to be aggregates of the
primary particles. X-ray diffraction patterns of precipitated plutonium show a faint
PuO2 structure, suggesting that the hydroxide is in reality hydrated PuO2 rather
than Pu(IV) hydroxide. The precipitate becomes more crystalline when aged at
elevated temperatures (Haire et al. 1971). Similarly the precipitates aged in a basic
or neutral medium display a crystalline pattern that corresponds to the cubic PuO2
structure and was confirmed by electron diffraction pattern. Colloids formed in
highly acidic media differ from those formed at higher pH (Bell et al. 1973). Thus
colloid morphology varies strongly depending on the method of preparation,
conditions of formation, and age of the solutions. For instance, fast neutralization
of Pu(IV) solutions with a base or water usually forms less ordered structures
(Reed et al. 2006). Scanning electron microscopy (SEM) and transmission electron
microscopic (TEM) images show amorphous morphology for these polymers (Neu
et al. 1997). The IR spectrum of Pu(IV) polymer showed major bands at 360 and
3400 cm1. They are assigned to Pu-O vibration similar to crystalline PuO2 and to
OH stretching vibration of a water group which is either hydrated or occluded in
the polymer structure. The comparison of the IR spectrum of PuO2 and the Pu
(IV) polymer precipitated and dried in air showed close resemblance of the
polymer bands in the 250–600 cm1 region suggesting a similar lattice structure
in the two compounds. Unlike PuO2, water and possibly hydroxyl groups are
present in the polymer (Toth and Friedman 1978). The size of Pu(IV) colloids
ranges from a few nanometers to almost micrometers, depending on the conditions
of generation (Lloyd and Haire 1978; Triay et al. 1991). Electron micrograph
shows that the primary particles are extremely small of the order of 5–20 Å
whereas the amorphous primary particles are of the order of 10 Å (Lloyd and
Haire 1973). TEM analysis of dried solutions shows evidence of small PuO2-like
clusters with a diameter of about 2 nm. LIBD experiments gave mean particle size
Fig. 5 TEM image of (a) intrinsic Pu nanocolloid cluster. (b) TEM image of intrinsic Pu
nanocolloid and tubular crystal of goethite (Powell et al. 2011)
of 5–12 nm. Particle size may increase to the point of precipitation. In acidic
solutions (pH 0.4–1) the weighted mean colloid size increases from 12 to 25 nm
with increasing degree of oversaturation with respect to amorphous Pu
(IV) hydroxide. They are said to be composed of small crystalline particle covered
by an amorphous layer (Walther and Denecke 2013). The small-angle X-ray
diffraction (SAXS) and XRD affirmed the presence of <40 Å PuO2 clusters.
Dynamic light scattering (DLS) and field flow fractionation (FFF) indicate that
the hydrodynamic radii of colloids vary on the order of 20–200 Å. Also the colloid
density is slightly lower than the density of PuO2 (Rundberg et al. 1987). As a
matter of fact, the size of plutonium colloids should increase with ageing time. But
in contrary, a recent report suggested that there was reduction in the size of 5-year-
aged colloid due to partial oxidation of Pu(IV) resulting in shorter Pu-O and Pu-Pu
bond distance. By means of TEM it was observed that Pu(IV) forms small
spherical PuO2 colloid of 2 nm. A recent TEM analysis on intrinsic plutonium
nanocolloids generated in the absence of goethite or quartz mineral shows 2–5 nm
diameter (Fig. 5a, b) (Powell et al. 2011).
Hydrolysis and Solubility of Pu(IV)
The hydrolysis reactions of Pu4+ ions are generally as in Eq. 10:
xPu4þ þ nH2 O , Pux ðOHÞ4xn

n þ nHþ (10)
The hydrolysis constants K0xn in a given medium and Koxn (at infinite dilution) are
given by Eq. 11:
h i
Pux ðOHÞðn4xnÞ ½Hþ
n
K o ðγ 4þ Þx ðaw Þn
K 0xn ¼ 4þ x ¼ xn Pu (11)
Pu γPux ðOHÞ4xn ðγH Þn
n
And the corresponding formation constants β0xy and βoxy:
h i
Pux ðOHÞ4xn
n βoxn ðγPu4þ Þx ðγOH Þn
β0xn ¼ 4þ x ¼ (12)
Pu ½OH n γ 4xn ðγ Þ
n
Pux ðOHÞn H
γ is the activity coefficient and aw is the activity of water. The value of log β011 was
found as 14.6 from experiments at trace levels of plutonium where the formation of
polymeric species is less likely (Metivier and Guillaumont 1972). Solubility of
tetravalent actinide is an important factor to be considered for mobility of plutonium
colloids in aquifer systems. Since Pu(IV) hydroxide phases or colloids span a wide
range of structural features and surface properties, such as amorphous/crystallin-
ities, size distributions (Fanghanel and Neck 2002), and stabilities it therefore
exhibits a wide range of solubilities (Neck and Kim 2001; Runde 2000) and thus
the reported solubility product shows considerable discrepancies (Kim and
Kanellekopulos 1989; Rai and Ryan 1982; Strickert et al. 1984). In general
the solubility products of the amorphous An(IV) hydroxide decrease in the series,
Th(IV) > U(IV) > Np(IV) > Pu(IV), due to decrease in An-O distance in the
lattice (Neck and Kim 2001; Guillaumont et al. 2003). The same trend is observed
for crystalline An(IV) dioxides. The solubility products Ksp0 and Kspo (at infinite
dilution) of amorphous Pu(IV) oxide or hydroxide, Pu(OH)4(am), are given by
Eq. 13:
PuðOHÞ4 ðamÞ , Pu4þ þ 4OH- (13)
0

K sp ¼ Pu4þ ½OH 4 and K sp
o 0
¼ K sp ðγPu Þ ðγOH Þ4
log Kspo for crystalline PuO2 is 64.0 and for amorphous hydrated hydroxide 58.3
[30]. Thus crystalline PuO2 is far less soluble than its amorphous hydroxide. The
slope of the solubility curve obtained from LIBD studies (Fig. 6) provides further
evidence that the dihydroxo-complex (Pu(OH)22+) is the prominent species in the
range of 1.0 < pHc < 1.6. The slope = 2 for the solubility curve infers that colloid
formation proceeds from Pu(OH)22+ via consumption of 2OH per Pu(IV) ion
suggesting Eq. 14 (Walther et al. 2007):
þ
PuðOHÞ2 2 þ 2OH $ PuðOHÞ4ðam=collÞ (14)
Fig. 6 Solubility of amorphous Pu(OH)4(am) comparing available literature data Walther et al.
(2007)
Methods Adopted to Remove Polymers
Two ways can be adopted to avoid the polymers formed in the system. They can be
either extracted or depolymerized.
Extraction of Pu(IV) Polymer/Colloid
Attempts were made to extract plutonium polymers or colloids using

neutral extractant TOPO (trioctylphosphine oxide), CMPO (octylphenyl-N,N-
diisobutylcarbamoylmethylphosphine oxide), and the bifunctional extractants
DHDECMP (dihexyl-N,N-diethylcarbamoylmethyl phosphonate). But in most of
the cases there is crud formation. They also co-extract other oxidation-state metals
(Muscatello et al. 1983). Back extraction of the polymer either was done in a silica
sol or required large concentrations of salts to reverse the extraction (Chaiko 1992).
A novel approach was made by dissolving the [Pu38O56Cl54(H2O)8]14 nanocluster
in aqueous solution of LiCl producing green solution of colloidal Pu which was
confirmed by the optical spectra. Addition of 6 M HCl changes green-colored

solution to red with change in the spectrum. The rapid change involves ion- or
ligand-exchange reaction between water and Cl. But the core moiety Pu38O56
remains unperturbed. Trichloroacetic acid (TCA) in n-octanol was chosen as
extractant due to its immiscibility with water. The well-defined surface of Pu
colloids can be altered and manipulated which can involve in ion- and ligand-
exchange reactions resulting in selective extraction of only plutonium colloid
leaving other plutonium species in aqueous phase.
Depolymerization
Depolymerization of plutonium polymer is a slow process. Freshly formed polymer

can be depolymerized whereas aged or polymers heated to higher temperatures are
difficult to depolymerize and it needs drastic conditions. In other words it leads to
very low depolymerization rates due to conversion of amorphous to crystalline
primary particles which involves more extensive cross-linking (Hunter and Ross
1991; Brunstad 1959). Some of the reported methods applied for depolymerizing the
polymer if formed accidentally are listed below.
Proposed Methods for Depolymerizing Pu(IV) Polymer
• Pu(IV) polymers can be depolymerized in the presence of reductants and oxidants

such as hydroquinone, H2O2, hydroxylamine, U(IV) and KMnO4, H2O2 + Fe
(NO3)3, Na2S2O8 + catalysts, and Co(III) in 0.533 M HNO3. This is because Pu
(III) and Pu(VI) formed due to reduction and oxidation are not prone to polymer-
ization (Ermolaev et al. 2001; Oak et al. 1983).
• Passing direct current through an aqueous nitric acid solution which contains
Pu(IV) polymer converts the polymer to Pu3+ and PuO22+ ions in turn are
converted to Pu4+ ions in the solution, followed by the step in which Pu4+ ions
are extracted from the solution. This can be done by contacting the acid solution
with a solution containing about 30% tri-n-butyl phosphate and 70% hydrocarbon
diluent (such as dodecane). It can also be done with ion-exchange resin (Tallent
et al. 1982).
• To avoid the complications of colloid formation, plutonium has often been
injected as the citrate complex, prepared by adding Pu(NO3)4 in concentrated
nitric acid to a 0.3–2.0% solution of trisodium citrate followed by adjustment with
base to pH 4–7. The rate of depolymerization is directly proportional to citrate
concentration, time, and acidity (Lindenbaum and Westfall 1965).
• Depolymerization is accelerated by introducing fluoride, sulfate, and other ions
forming strong complexes with Pu4+ (Weigel et al. 1997).
• The process of depolymerization is accelerated on exposure to UV radiation (Bell
and Friedman 1976; Friedman et al. 1977).
Uranyl Nitrate Effect
• Solutions of plutonium are commonly used in the presence of large amounts of

U. Therefore the effect of uranyl ion on the polymer chemistry is of consid-
erable interest. Much uncertainty exists about the effect of UO2(NO3)2 on the
formation rate of Pu(IV) polymer because this solute provides nitrate ions
which could either complex with Pu(IV) and stabilize it with respect to
hydrolysis and polymerization or, through complexation with Pu(IV), shift
the disproportionation equilibrium to the left, thereby decreasing the real
acid concentration of the solution and causing a corresponding increase in
the rate of hydrolysis and polymerization. UO22+ functions as a chain termi-
nator through the formation of hydroxyl bridges to terminal uranyl groups
(Quiles and Burneau 1998). Also, Pu(IV) polymer formed in the presence of
uranium is shorter than those which are formed in the absence of uranium.
This shows that presence of uranium in a polymerizing Pu(IV) solution
reduces the rate of polymer formation about 30% without appreciably entering
the polymer.
• Costanzo and Biggers (1963) prepared polymer in 5 N HNO3 and aged for several
months. It is observed that for aged polymers the depolymerization halftime is
320 h and it is only 20 h for freshly prepared polymer.
• Depolymerization occurs easily at 90 C in 6 M HNO3. Also, Pu(IV) polymer can
be dissolved using Na2S2O8. Decomposition of S2O8 yields H2SO4 favoring
Pu(IV) depolymerization (Savage and Kyffin 1986).
Hydrolysis of Th(IV)
Th(IV) exhibits a strong tendency towards hydrolysis and subsequent polymeriza-

tion over a wide range of pH and concentrations. Thorium has an ionic radius of
1.09 Å in nine coordinations making it the largest stable tetravalent metal ion and in
spite of its high valence it is least susceptible to hydrolyze when compared to U
(IV) or Pu(IV) (Torapava et al. 2009). Many studies have reported Th
(IV) hydrolysis and the species formed in solution depending on pH and concen-
tration. Th4+(aq) ion can be found as a predominant species only at pH < 3. It has
been observed that mononuclear ionic complexes dominate the species distribution
at very low concentrations as well as at high acidity (Khazaei et al. 2011). At near-
neutral pH, and as the thorium concentration approaches the solubility limit of the
amorphous hydroxide Th(OH)4, polymers become the dominant species in solu-
tion, starting with dimers which grow and form pentamers. Pentamers have been
found to be the most abundant and stable complex rather than tetramers and
hexamers (Walther et al. 2012). The polymeric species are found to contain one
or more thorium atoms linked by hydroxy bridges (Bacon and Brown 1969). With
increasing pH and thorium concentration it forms thorium nanoparticles or the
so-called colloids.
Probing the Formation and Structure of Th(IV) Hydrolyzed Species
Th(IV) hydrolysis and polymerization reactions follow the same pattern as Pu(IV).
Th(IV) colloid formation is preceded by polynuclear hydroxide complexes such as
Th2(OH)26+, Th2(OH)35+, Th4(OH)88+, Th4(OH)128+, Th6(OH)1410+, and
Th6(OH)159+. But in contrast to Pu(IV) polynuclear hydroxide complexes, Th
(IV) polynuclear hydroxide complexes are thermodynamically unstable (Walther
et al. 2008). Structural studies on aqueous solution of the hydrolysis products of Th
(IV) have identified three different types of hydrolysis species: a μ2O-hydroxo
dimer, [Th2(OH)2(H2O)12]6+; a μ2O-hydroxo tetramer, [Th4(OH)8(H2O)16]8+; and
a μ3O-oxo hexamer, [Th6O8(H2O)n]8+ (Rand et al. 2007). Single crystals of oxo- and
hydroxo-bridged haxameric [Th6(μ3-O)4(μ3-OH)4]12+ (Takao et al. 2009; Knope
et al. 2011) and octameric [Th8O4(OH)8]16+ (Knope et al. 2012) have also been
isolated by addition of complexing ligands. SAXS investigation revealed the pres-
ence of microcrystalline particles with the thorium oxide structure in highly hydro-
lyzed Th(IV) solutions (Magini et al. 1976). In another study, when a thorium
chloride solution was left to evaporate at room temperature, it produced hydroxo-
bridged Th dimers. Thorium structure of Th(IV) pentamers was investigated by
XAFS and by quantum chemical calculations. It was considered that the most
favorable structure contains two Th(IV) dimers linked by a central Th(IV) cation
through hydroxide bridges. These polymers are then subjected to continuous hydro-
lysis; that is, the number of hydroxide ligands increases with increase in pH. The
ultimate end product of Th hydrolysis is an oxo-bridged ThO2 with fluorite structure
(Sellers et al. 1954).
Size and Morphology of Hydrolyzed Th(IV) Polymer/Colloid
Freshly formed small particles have a mean diameter in the range of 16–23 nm
(Rothe et al. 2002; Bundschuh et al. 2000). Three different oxides/oxo-hydroxide
solid phases have been reported for thorium, that is, crystalline ThO2 whose particle
size is >50 nm, microcrystalline ThO2.xH2O of 15–30 nm, and amorphous ThO2.
xH2O of 2–5 nm. Upon heating a highly hydrolyzed thorium solution the particle
size was estimated to reach as large as 20–50 Å in diameter. But if that same solution
was left to age without evaporation it produced small ThO2 particles with sizes of
about 20 Å. The small 20 Å ThO2 particles are X-ray amorphous (Neck et al. 2002).
DLS measurement shows that well-defined colloids were formed at two different pH
domains. The colloids formed at pH~0.8 were smaller, when compared to those
formed at pH~2 (Priyadarshini et al. 2016).
Hydrolysis and Solubility of Th(IV)
M-O bond length of Th(IV) is largest compared to Pu(IV) due to actinide contraction
and hence anionic ligand forms much stronger for Pu(IV) than for Th(IV).
Accordingly the first hydrolysis constant of Th(IV) is smaller than Pu(IV). Some of
the reported values of formation constants for the first mononuclear hydroxide
complex M(OH)3+ are logβ1,1 = 11.8 0.2 and logβ1,1 = 11.5 0.5. In order
to measure the solubilities, two regions with respect to pH and Th(IV) concentration
need to be considered, which correspond to different solid phases, microcrystalline
and X-ray amorphous ThO2 (Ekberg et al. 2000). Rai et al. (2000) determined the
solubility product of crystalline ThO2 in acidic solution (pH < 2.5) as log
Kspo = 54.2 1.3. A combined coulometric and pH titration in the pH range
1.5–2.5 with LIBD gave a solubility product of log Kspo = 52.8 0.3. The
ambiguity in the solubility data is mainly due to the presence of polynuclear species
or intrinsic colloids prevailing in the system. With increase in pH and close to the
solubility limit, where Th(OH)4 is the predominant aqueous species, the solubility
product of crystalline ThO2 is similar to that of amorphous ThO2 (log Ksp (Th(OH)4
(am;hyd)) = 47.8). Hence it can be concluded that in near-neutral solutions the
bulk crystalline ThO2 is covered with an amorphous and more soluble surface layer.
Solubility studies conducted on Th(IV) intrinsic colloids in concentrated NaCl (0.5
and 5.0 M) and MgCl2 (0.25, 2.5, and 4.5 M) solutions within the pH range 8.8–10.8
revealed that the hydrophilic oxo-hydroxide intrinsic colloids formed through chem-
ical polynucleation reactions are stable equilibrium species and contribute to the total
solubility of Th(IV).
Stability of Th(IV) Hydrolyzed Colloids
Laser-induced breakdown (LIBD) spectroscopy combined with ultrafiltration was

used to investigate the generation of Th(IV) colloids in the concentration range from
105 to 102 M at pH 3–5 in 0.5 M NaCl. Surprisingly the colloids generated by
coulometric titration are found to be small in size and remain stable up to 400 days of
investigation, without a tendency towards agglomeration or precipitation. There was
no change in size and concentration of colloids during the course of investigation
which shows their extreme stability. These suspensions on dilution lead to an
equilibrium between colloids and ionic species (Bitea et al. 2003a).
Uranyl Effect on Polymerization of Th(IV)
Previously it was shown that the presence of uranyl ion retards the rate of Pu
(IV) hydrous polymer formation. Raman spectroscopic studies were done on Th
(IV) in order to characterize the uranyl-thorium(IV) interaction. By monitoring the
changes in the frequency of the uranyl symmetric stretching vibration, that is, the
shift in 869 cm1, Raman band corresponding to unassociated UO22+ to 851 cm1
for UO22+ attached to Th(IV) polymer. In the same solutions when aged, there was
change in bridging structure (i.e., hydroxyl to oxygen) which was confirmed by the
appearance of band at 665 cm1 and by the change in color of dispersed polymer
from a uranyl pale yellow to a urinate golden orange (Toth et al. 1984).
Molecular Weight of Th(IV) Hydrolyzed Polymer
Static light scattering measurements showed that the Th(IV) colloids formed at pH
~0.8 have a molecular weight of ~3449 Da and it shows that ~15 Th atoms are present
in the polymeric network at the initial stage. The second virial coefficient is negative. It
implies that there was aggregation in the system leading to precipitation. The colloids
formed at acidic pH tend to agglomerate causing precipitation in the system. But, the
colloids formed at pH > 2.0 have a molecular weight of ~6223 Da with positive second
virial coefficient. This polymeric colloid formed due to polynucleation contains around
20 atoms of Th when initially formed. The solute-solvent interaction in the system is
higher leading to greater stability of the system. The colloids upon ageing for 7 days did
not show any considerable change in their molecular weight but when it was aged for
55 days the molecular weight increased to 43,573 Da (Priyadarshini et al. 2016).
Uranium
In nuclear reactors, uranium is handled in large quantities when compared to other

actinide elements. The behavior of uranium in radioactive waste repositories and the
migration of uranium in the environment depend on its oxidation state and its
speciation is determined by pH, presence of complexing anions, and total salt
background. Uranium exists in different oxidation states (from +3 to +6). The
known redox states of uranium are U(II), U(III), U(IV), U(V), and U(VI) and their
corresponding reduction potentials are given in Fig. 7.
Uranium(III) can exist only under anaerobic and strongly reducing conditions.
U(IV) is also considered as toxic waste under strongly reducing conditions that is
often accepted to be present in deep geological repositories. U(V) is unstable and
disproportionates. U(VI) is the most common species in the environment. Under
natural aquatic systems, uranium exists as U(IV) and U(VI).
Hydrolysis and Polymerization of Uranium(IV)
The known redox states of uranium are U(II), U(III), U(IV), U(V), and U(VI). U
(IV) aqueous chemistry is of particular interest under reducing conditions which
prevails in both inside of nuclear waste repositories and under deep uranium mines.
Due to hydrolysis, U(IV) occurs in the form of [U(OH)x](4x)+. The hydrolysis
-1.60 V
0.19 V 0.37 V -0.61 V -4.7 V -0.1 V

2+ UO2+ 4+ U3+ U2+
UO2 U U
0.28 V -1.35 V
Fig. 7 The redox potential differences for the uranium ions and pure U
reactions of U(IV) resulting in the formation of polynuclear hydrolysis complexes

are given in Eq. 15:
4þ h ið4xyÞþ
x UðH2 OÞn þ yH2 O , Ux ðOHÞy ðH2 OÞny þ yH3 Oþ (15)
U(IV) is readily oxidized to U(VI) when reducing conditions are not maintained
carefully. Due to hydrolysis U(IV) occurs in the form of [U(OH)x](4x)+. There are
limited literature data on hydrolysis studies on U(IV).
Probing the Formation and Structure of U(IV) Hydroxide/Oxide
In contrast to UO22+ for which several oxides and hydroxides are known, only few
U(IV) oxide/hydroxide structures are known. Uranium(IV) dioxide adopts a fluorite
structure. The compound prepared by hydrothermal hydrolysis of a U(IV) sulfate
solution at 100–150 C showed a structure isostructural with that described for
thorium and consists of infinite chains of hydroxo-bridged (U(OH)2)n2n+ units with
UU distances of 3.90 Å.
Size and Morphology of U(IV) Colloid
Attempts were made to produce colloids of U(IV) by electrochemical reduction of U

(VI). EXAFS investigations were performed and compared with solid UO2 and
amorphous UO2.nH2O. They showed correspondence with the latter (Opel et al.
2007). Around 20 nm colloidal particle was detected in 2.5 mM U(IV) solutions at
pH ~3.6 by DLS experiment. It decreased to ~5 nm when the concentration of U
(IV) was increased to 19 mM (Priyadarshini et al. 2014).
Hydrolysis and Solubility of U(IV)
The solubility product of crystalline UO2(cr) formed at pH ~1 and amorphous

hydrous oxide UO2.xH2O(am) formed at pH ~3 was determined by combined
coulometric titration and LIBID experiments as log Kspo = 59.6 1 and log
Kspo = 54.1 1 (Manfredi et al. 2006). Compounds containing U(IV) are
insoluble in mildly acidic and alkaline medium. U(OH)2SO4 was prepared at
100–150 C from the hydrothermal hydrolysis of a U(IV) sulfate solution. The
structure is isostructural with that described for thorium and consists of infinite
chains of hydroxo-bridged (U(OH)2)n2n+ units (Qiu and Burns 2013).
Molecular Weight of Hydrolyzed U(IV) Polymer
Light scattering measurements performed on freshly formed polymers of U(IV)

showed a weight average molecular weight (Mw) of 1820 Da and it increased to
13,000 Da when aged for 3 days. Around 40–50 atoms of U are considered to be
present in the aged polymer. Positive value of second virial coefficient shows that the
solute-solvent interaction is high leading to stable suspension of aged polymers
(Priyadarshini et al. 2014).
Hydrolysis of Uranium(VI)
Under aerobic conditions, hexavalent uranium is more relevant in aqueous medium.

U(VI) is thermodynamically most stable form with relatively high solubility (Zanker
et al. 2007; Zhao and Steward 1997). Being a hard Lewis acid, it shows strong
interactions with hard donor ligands resulting in a tendency to undergo hydrolysis,
formation of soluble complexes with carbonates and phosphates, and the most
important is its ability to form colloids which will increase the migration behavior
in natural systems (Eliet and Bidoglio 1998). Hence it becomes mandatory to study
the speciation and related reaction products of uranium in aqueous systems, under
well-defined conditions such as pH, ionic strength, concentration, and presence of
other ligands. The hydrolysis equilibrium reaction of uranyl ion in general can be
written as given in Eq. 16:
ð2mnÞþ
2 þ nH2 O , ðUO2 Þm ðOHÞn
mUO2þ þ nHþ (16)
The solution chemistry of U(VI) is dominated by the linear dioxo cation UO22+
(Kirishima et al. 2004). In aerated aqueous solutions at pH 2.5, the uranyl ion is very
stable. The hydrolysis of uranyl ion starts at pH values greater than 3 (Clark et al. 1999)
and also if the concentration of uranyl exceeds 103 M (Steppert et al. 2012). UO2OH+
is the only mononuclear hydrolysis product present at appreciable concentration up to
pH ~7 in 105 M or more concentrated U(VI) solutions (Brooker et al. 1979). The well-
established dinuclear species (UO2)2(OH)22+ is present over the pH range of 3–6 and
accounts for at most 40% of the total U(VI) in 102 M solutions. (UO2)3(OH)5+,
(UO2)4(OH)7+, and (UO2)3(OH)7 are the dominant polynuclear species from pH 5 to
9 in solutions of 102 to 105 M U(VI), accounting for up to 100% of the total uranium
in solution. Potentiometric measurement (Palmer and Nguyen-Trung 1995), time-
resolved fluorescence spectroscopy (Eliet et al. 2000), Raman spectroscopy (Quiles
and Burneau 2000), attenuated total reflection infrared (Muller et al. 2008), and
electrospray mass spectrometry (Clark et al. 1999) studies reveal that in acidic solutions
of pH levels (2 pH 5) UO22+, (UO2)2(OH)22+, and (UO2)3(OH)5+ are the
predominant species. Complexes (UO2)3(OH)7, (UO2)3(OH)82, (UO2)3(OH)104,
(UO2)3(OH)115, and (UO2)3(OH)42 have also been suggested by various methods
(Kirishima et al. 2004). There is consensus that several polynuclear species coexist in
alkaline solution. A number of structures that contain chains or extended structures of
hydroxo- and oxo-bridged UO22+ have been reported.
The hydrolyzed U(VI) species aggregate and reach colloidal dimensions and exist
as suspended sols in the aqueous medium. Particle size is an important property to
Fig. 8 Speciation diagram of

UO2(CO3)34–
U(VI) ions as a function of pH 100
UO2(CO3)(OH)3–
in aqueous solution at UO22+
Relative distribution (%)

atmospheric condition (Scierz
and Zanker 2009) 80
60 β-UO2(OH)2(s)
+
40 (UO2)3(OH)5
UO2(CO3)22–
+
20 UO2(OH)
0
3 4 5 6 7 8 9 10
pH
define a colloidal system. It influences the behavior of colloids during diffusion,

aggregation, etc. DLS studies were performed on different concentrations of uranyl
solution diluted to neutral pH. A peak around 32–36 nm was observed on all the
concentration range of U(VI) in DLS (Priyadarshini et al. 2014). Hence it has been
confirmed that the colloids have size of ~32–36 nm. With increasing concentration
of uranyl ions the pH for colloid formation decreases considerably. The colloids
formed were not stable for a long period of time. There is no change in average
particle size of the colloids as the concentration of U(VI) increases. Well-defined
colloids are formed when the concentration reaches the precipitation point. The
molecular weight of U(VI) colloid was determined as ~763 Da which was much
less when compared to U(IV) and Pu(IV) (Priyadarshini et al. 2014). The calculated
molecular weight shows that there may be 2–3 units of uranyl groups bridged by
hydroxyl groups. Hence it is only oligomer that has been formed. Figure 8 represents
the relative abundance of U(VI) species as a function of pH in the aqueous solution
at atmospheric normal environmental.
Nanomaterials for Separation of Actinides
Safe management of radioactive waste with minimum impact to environment is

emerging as one of the major challenges in separation science. Accumulation of
large volume of the radioactive wastes is highly risky. The risk is directly propor-
tional to volume of the waste. Therefore, these waste streams need to be treated to
reduce their activity to a level at which they are permitted as per national regulations.
This leads to more demanding efforts in removal of radionuclides from aqueous
solution for environmental concern. It is one of the most urgent technological
problems that mankind face worldwide. Decay is the only natural way of reducing
radioactivity. Since radionuclides have decay rates ranging from seconds to thou-
sands of years, proper segregation of wastes depending on their half-lives and
conditioning is an important factor. The major aim is to separate long-lived alpha-

emitting actinide radionuclides. Hence, safe and efficient management of long-lived
actinide is of utmost importance. Under this situation, versatile materials and
technologies that can remove the radionuclides and remediate the environment are
of severe demand. Although a wide range of separation techniques are employed for
removal of radionuclide, amalgamation of nanotechnology into conventional tech-
niques has revolutionized the separation processes. Nanomaterials offer high surface
area, high sorption capacities, selectivity, and reusability (Dash and Chakravarty
2017). In recent years, nanomaterials such as carbon nanostructures, meso porous
materials, and nanopolymers/dendrimers have been extensively investigated for
actinide separation. The potential application of aforementioned nanomaterials in
removal of long-lived actinides from aqueous media is briefly discussed in this
chapter.
Carbon Nanostructures
Carbon nanostructures, including carbon nanotubes (CNTs), nanodiamonds, fuller-

enes, graphene, and other carbon materials, have been the most effective materials
for environmental remediation, and have attracted great attention recently. The large
specific surface area, the outstanding thermal and chemical stabilities, and the recent
development in large-scale synthesis make carbon nanostructures attractive as inter-
esting possible solid-phase extraction (SPE) materials (sorbents) for treatment of
radioactive waste. Various types of bulk sorbents such as organic (Sureshkumar et al.
2010), inorganic (Li et al. 2012), biosorbent (Ghasemi et al. 2011), composites (Gao
et al. 2010), and other carbon-based material (Starvin and Rao 2004) have been
developed for the recovery of radionuclides from aqueous systems. However, the
low sorption capacities or efficiencies of these materials have obviously restricted
their applications. Search for alternatives to conventional bulk adsorbents has
intrigued intense interest on use of nanomaterial-based adsorbents due to their
unique physicochemical properties as compared to their bulk equivalents. Nano-
materials circumvent many limitations of bulk material-based adsorbents. Carbon
nanostructure characteristics such as large surface area, high specificity, fast adsorp-
tion kinetics, and ability to interact with different chemical species make them
excellent candidates for radionuclide separation.
Carbon Nanotubes (CNTs)
Carbon nanotube (CNT) is a well-known carbon nanostructure. CNTs can be

described as a graphite sheet rolled up into a nanoscale tube; they are typically
several nanometers (nm) in diameter and both ends are normally capped by
fullerene-like structures. There are two main types of CNTs: (i) single-walled
CNTs and (ii) multi-walled CNTs named based on the number of graphene sheet.
CNTs exhibit unique properties such as strong tensile strength, large elastic module,
high heat conductivity and electrical conductibility, and large surface area (Belloni et al.
2009). Due to its extraordinary physicochemical properties, CNTs have been widely
applied in various scientific areas such as electronic, power engineering, medical, and
catalysis. With a continuously decreasing cost of production and required properties
(large surface area, hollow structure, strong affinity for ionic and organic species,
chemical and radiation stability), its application has been stretched to sorbent material
for extraction of radionuclides. For example, pristine MWCNTs were investigated as a
sorbent for europium (Tan et al. 2008), americium (III) (Wang et al. 2005), thorium
(Chen et al. 2007a), uranium, and plutonium radionuclides due to the strong complex-
ation of sorbates on the MWCNT surface in the aqueous and NaClO4 medium.
Functional groups like –COOH, –C=O, and –OH are incorporated on the surface of
MWCNTs by treating with strong oxidizing agents like conc.HNO3 or mixture of conc.
HNO3 and conc.H2SO4 at elevated temperature (Chen et al. 2007b; Darmstadt et al.
2003). The oxidized MWCNTs offer a more hydrophilicity and surface area. The
oxidized MWCNTs show fast kinetics and a high sorption activity towards uranium,
thorium, and plutonium radionuclides in weakly acidic to weakly basic solutions
(pH 3–8) (Myasoedova et al. 2009). The pH of aqueous solution plays an important
role; it influences both the metal ion speciation and total surface charge on sorbents. The
isoelectric point of pristine and oxidized MWCNTs is ~7.1 and ~5, respectively (Wang
et al. 2005). The isoelectric point of MWCNTs (ξ-potential) depends on their prepara-
tion, pretreatment methods, and different functionalities on MWCNTs. At pH less than
isoelectric point (ξ-potential), the surface of MWCNTs is positively charged due to
protonation reaction and negatively charged due to deprotonation at pH greater than
isoelectric point. The electrostatic repulsion between the positively charged surface of
the sorbent and positively charged species of uranium/thorium/plutonium resulted in a
very low sorption capacity at lower pH. In the pH range of 5–8, the transition in the
surface polarity of MWCNTs favored the sorption of hydrolyzed species of uranium
(UO2(OH)+, (UO2)2(OH)22+, (UO2)3(OH)5+, UO2(OH)2)/thorium (Th(OH)3+, Th
(OH)22+, and Th(OH)4) and maximized the uptake capacity. But at higher pH values
(pH > 8), the electrostatic repulsion between the negatively charged MWCNTs surface
and the negatively charged uranium species (UO2(CO3)22 and UO2(CO3)34) resulted
in a rapid decrease in sorption. In case of thorium at pH > 4, deposition of precipitated
thorium complexes onto the MWCNTs resulted in decrease of sorption. Plutonium is
known to take part in disproportionation, hydrolysis, and polymerization reactions and
form concurrently polymeric forms in different oxidation states (Walther 2008). The
oxidized CNTs are capable of extracting both the polymeric Pu4+ and ionic forms (Pu3+,
Pu4+, PuO2+, PuO22+) from weakly acidic to weakly basic solutions (Perevalov and
Molochnikova 2009). Pu sorption on oxidized MWCNTs follows the Pu4+ > PuO22+
> PuO2+ trend due to their charges. Both the pristine- and acid-pretreated CNTs were
found to be useful for actinide sorption; however their removal efficiency and selec-
tivity towards particular radionuclides remain quite limited. In recent years, much
attention has been diverted towards making the MWCNTs highly selective and less
hydrophobic. Due to higher hydrophobicity, the dispersion of MWCNTs in an aqueous
medium is less, resulting in aggregation of MWCNTs due to van der Waals interaction
and thus hindering in the sorption process to a greater extent. To enhance the
dispersibility in aqueous solution, sorption performance, and selectivity towards par-

ticular radionuclides, CNTs have been functionalized without much alteration of their
physical and chemical properties. Modification of CNTs is accomplished through
covalent or noncovalent functionalization. MWCNTs were easily dispersed in solution
by plasma-induced grafting of carboxymethyl cellulose on MWCNT (MWCNT-g-
CMC). MWCNT-g-CMC has much higher adsorption capacity for U(VI) compared to
the raw MWCNTor oxidized MWCNT (Wang et al. 2009). Similarly, MWCNTs grafted
with chitosan (MWCNT-g-CS) showed high sorption performance for uranium (Shao
et al. 2010).
MWCNTs functionalized with organic ligands are shown to be more selective than
pristine and oxidized MWCNTs. Specifically, the CNTs are functionalized with
amide- and phosphorus-based organic ligands used in the liquid extraction. The
sorption behavior of functionalized MWCNTs depends on the functionality and the
mechanism adopted for the sorption. Sorption performances of diglycolic acid
(DGA)-functionalized MWCNTs (DGA-MWCNTs) (Deb et al. 2012, 2013) have
been evaluated for U(VI) and Th(IV) in aqueous solution. The sorption behavior of U
(VI) and Th(IV) on DGA-MWCNTs is highly influenced by pH of the solution.
Effective sorption of U(VI) and Th(IV) on DGA-MWCNTs was found to be at
pH 5–7 and 4, respectively. DGA-MWCNTs have been investigated for U(VI), Am
(III), and Pu(IV) from nitric acidic medium (Sengupta et al. 2017a; Deb et al. 2012).
The sorption of U(VI), Am(III), and Pu(IV) increases gradually with nitric acid
concentration and reaches maximum at 3–5 M HNO3. Further increase in acid
concentration does not alter much the sorption. At acidic condition (pH < 2), DGA
group in MWCNTs remains unionized and acts as neutral chelating group which can
bind effectively with neutral metal nitrate species. The increase in formation of
M(NO3)n (Pu(NO3)4, Am(NO3)3, UO2(NO3)2) species with nitric acid concentration
effectively coordinates with DGA group; thereby increase in sorption was observed:

Mnþ þ nNO3 $ MðNO3 Þn M ¼ Am3þ =Pu4þ =UO2 2þ and n ¼ charge (17)
MðNO3 Þn þ DGA-MWCNTs $ MðNO3 Þn :DGA-MWCNTs (18)
Sorption of U(VI), Pu(VI), Am(III), and Pu(IV) on dihexylamide (DHA)-

functionalized MWCNTs (DHA-MWCNTs) also found to be increasing with nitric
acid concentration (Gupta et al. 2017b). However, DHA-MWCNTs have shown low
sorption performance for UO22+ and Th4+ compared to DGA-MWCNTs. Sorption of
Pu4+ or Am3+ on poly(amidoamine) (PAMAM) dendrimer of generation 1 and
2 functionalized MWCNTs (MWCNT-PAMAMG1 and MWCNT-PAMAMG2)
was studied (Kumar et al. 2017). PAMAM-functionalized MWCNTs (MWCNT-
PAMAMG1 and MWCNT-PAMAMG2) have shown much higher sorption capacity
for Pu4+ and Am3+ compared to DGA-MWCNT or DHA-MWCNT sorbents.
PAMAM dendrimer has more number of amide and amine functional groups and
they increase with dendrimer generation MWCNT-PAMAMG(n = 1,2. . .). These
amide and amine functional group of PAMAM forms strong complex with f-block
element leads to have higher sorption capacity than other functionalized MWCNTs.
The amidoamine-functionalized MWCNTs (MWCNT-AA) were also employed

for the sorption of Pu4+,NpO2+, PuO22+, and NpO22+ in an acidic aqueous medium
(Sengupta et al. 2017b). In aqueous medium neptunium exists as NpO2+ without
disproportion with lower chemical potential making it very difficult to separate.
However, the sorption performance of MWCNT-AA for Np was found ten times
higher than ligand-impregnated MWCNTs making it an efficient solid-phase sorbent
for the separation of Np from nuclear waste solution. The sorption of neptunium
species (NpO2+ and NpO22+) increases with increase in aqueous nitric acid concen-
tration and remains almost constant above 3M HNO3 concentration. However, an
exponential increase in sorption of Pu4+ and PuO22+ on MWCNT-AA was observed
with aqueous nitric acid concentration (Sengupta et al. 2017b).
Ligand-Impregnated MWCNTs
Ligands which showed high distribution coefficient along with selectivity for a
particular oxidation state of actinides in liquid–liquid extraction have been impreg-
nated on MWCNTs. Various phosphorus-based ligands like diphenyl
(dibutylcarbamoylmethyl) phosphine oxide (CMPO), tri-n-octylphosphine oxide
(TOPO), tri-n-butylphosphate (TBP) [Murali and Mathur 2001; Yaftian et al. 2003],
nitrogen-based ligands like N,N‘-dimethyl-N,N‘-dioctylhexylethoxymalonamide
(DMDOHEMA) (Serrano-Purroy et al. 2005), and task-specific ionic liquids like
tetra alkyl ammonium hydrogen phthalate (Gupta et al. 2017a) and phosphonium
ionic liquid Cyphos IL-101 (Quinn et al. 2013) were shown distribution ratio and
selectivity towards actinides in the presence of various other fission products. Hence,
these ligands were impregnated on the MWCNTs by stirring a suspension of
MWCNTs and a ligand directly in nitric acid solution. Impregnation is mostly a
combination of pore filling and surface adsorption. The extractant gradually fills the
pore space starting with the smallest pores and moving up to pores of about 10 nm and
then surface adsorption becomes the dominant force. Interaction between the extra-
ctant and support is usually quite weak, consisting of only the attractive forces between
alkyl chains and/or aromatic rings of the ligand and those of the support.
The sorption of Np(V), U(VI), Pu(IV), Am(III), and Eu(III) onto CMPO-, TOPO-,
and Cyphos IL-101-impregnated MWCNTs (Taunit) had shown some promising
results in nitric acid solution (Zakharchenko et al. 2012). Taunit-TBP and Taunit-
DMDOHEMA sorbents are also useful for the separation of plutonium from acidic
nuclear waste solution (Zakharchenko et al. 2012).
Graphene Oxide (GO)
Graphene oxide (GO) is one of the most important graphene derivatives. It has
unique structure and exceptional physicochemical properties. The remarkable prop-
erties of graphene include high Young’s modulus, fracture strength, thermal con-
ductivity, mobility of charge carriers, specific surface area (theoretical calculated
value of 2630 m2 g1), high chemical stability, large pore volume structure, and
fascinating transport phenomena (Chen et al. 2012). GO has many oxygen-
containing functional groups in the form of epoxy, hydroxyl, and carboxyl groups
on its basal plane and edges. These oxygen-containing groups can bind metal ions
and organic pollutants through coordination, electrostatic interaction, hydrogen
bonding, etc., which ensures its potential application in environmental remediation
(Nupearachchia et al. 2017).
GO is hydrophilic in nature due to existence of many oxygen-containing func-
tional groups. In addition, the delocalized π electron systems of graphene layer as
Lewis base can form electron donor–acceptor complexes with radionuclides as
Lewis acid through Lewis acid–base interaction. The U(VI), Am(III), Sr(II), and
Pu(IV) radionuclides were removed using GO sorbent (Romanchuk et al. 2013). GO
was shown as an efficient sorbent for Th(IV) due to large surface area and sufficient
exposure of active sites of abundant oxygen-containing functional groups with Th
(IV) (Bai et al. 2014). Removal of U(VI) ions from an aqueous system using
few-layered GO nanosheets was reported. However, the aggregation and accumula-
tion of few-layered GO nanosheets resulted in limited sorption of U(VI) which was
observed in the aqueous systems (Zhao et al. 2012). GO-based materials are easier to
process and easily functionalized. Therefore, polymers including polyaniline, poly-
acrylamide, cyclodextrins, chitosan, and amidoxime were grafted onto GOs to
introduce various functional groups and to enhance their dispersibility in solutions
and thereby improve the removal ability of some radionuclides (Wang et al. 2016).
Such approaches, which added functionality to groups already present on the GO
surfaces, make GO a more versatile sorbent (Dreyer et al. 2010). Cyclodextrin-
modified GO nanosheets (CD/GO) were synthesized using an in situ polymerization
method (Song et al. 2014). The mutual effects on the simultaneous removal of U
(VI) and humic acid from an aqueous system by CD/GO were investigated. The
sorption of U(VI) and humic acid (HA) sorption on CD/GO highly depend on pH
and ionic strength. The presence of HA enhanced U(VI) sorption at low pH and
reduced U(VI) sorption at high pH, while the presence of U(VI) enhanced HA
sorption.
Magnetic Nanoparticles for Sorption
Magnetite nanoparticles (MNPs) have received much attention recently to remove

radioactive metal ions due to the easy separation of sorbent from solution with the
aid of magnetic field. The bisphosphonate-modified magnetite Fe3O4 nanoparticles
were used to remove U(VI) from blood at pH 7.0 (Wang et al. 2006). However, the
Fe3O4 nanoparticles are unstable at acidic condition, which limits their application
for nuclide sorption from acid nuclear wastewater. Aggregation and decomposition
of Fe3O4 nanoparticles under extreme pH conditions hinder the separation process of
actinides. This situation can be circumvented by designing core-shell type of nano-
materials (Kaur et al. 2013a). The magnetic core material is protected by a shell
made up of nonmagnetic materials such as polymer, silica, carbon, and gold. This
sort of core-shell dimension reduces aggregation as well as improves extraction

efficiency. For instance, silica-coated magnetic nanoparticles were developed for the
separation of actinides from acidic nuclear waste, in which the Fe2O3 nanoparticles
were coated with the silica, followed by covalent attachment of the actinide-specific
chelators. The silica-coated MNPs are stable even in 1 M HCl solution, and show
enhanced actinide separation efficiency compared to the uncoated counterparts (Han
et al. 2010).
The affinity of the magnetic nanoparticle towards a particular metal ion is
enhanced by functionalizing it with -thiol, -amine, and -carboxyl functional groups.
These functional groups provide active sites for the capture of metal ions which get
complexed by chelate formation, ion-exchange process, or electrostatic interactions.
Therefore, surface-functionalized Fe3O4 magnetic nanoparticles are preferred over
pristine Fe3O4 nanoparticles for the separation of metal ions (Singh et al. 2013). The
selectivity of the chelators towards particular metal ion can be tailored by selecting
ligands with oxygen, nitrogen, and sulfur donor atoms. This is done based on hard-
soft nature of donor atoms and metal ions. Generally hard and soft metal ions form
strong complexes with hard and soft ligands, respectively (Kaur et al. 2013a). This
concept is exploited for the selective extraction of metal ion using ligands.
Diethylene triamine penta acetic acid (DTPA) chelator covalently tethered to
silica-coated magnetic nanoparticles was found to be efficient for the recovery of
Am(III), Np(V), Pu(IV), and U(VI) under acidic conditions (Kaur et al. 2013b). N,N,
N0 ,N0 -tetraoctyl diglycolamide (TODGA)- and bis(2-ethylhexy)phosphoric acid
(HDEHP)-coated superparamagnetic Fe3O4 nanoparticles (NP) were investigated
for the extraction of Am(III) and Pu(IV) from the solution of 3–4 M HNO3 (Ojha
et al. 2017). TODGA-coated magnetic nanoparticles extracted both Am(III) and Pu
(IV) whereas HDEHP-coated magnetic nanoparticles selectively extracted Pu(IV).
This sort of magnetic nanoparticle-extractant framework can be effectively utilized
for the pre-concentration of metal ions followed by their easy separation.
Nanocomposites
Nanocomposite is a multiphase solid-state material with at least one of the phases in

nano-dimension which might be zero-dimensional (quantum dots) or
one-dimensional (nano rods) or two-dimensional (nanosheets) (Okpala 2013).
Also, the multiphase materials with their phases separated by a distance of nanoscale
are termed as nanocomposites. The idea of incorporating nanoscale materials is to
promote the synergism among the constituents that emerges into novel properties
capable of meeting desired specifications. Multifunctional capability of nano-
composites arises due to the benefit of nanoscale properties, huge interphase zone,
and chemical functionalization. Different types of metal-, carbon-, ceramic-, and
polymer-based nanocomposites possess a variety of properties (Camargo et al.
2009). The properties of nanocomposites can be modified by choosing the right
parameters. These parameters include nanoscale dimension, loading, degree of
dispersion, shape, orientation, matrix material, and interaction among the
constituents. These parameters are meticulously selected to prepare materials with

desired flexibility, ductility, strength, conductivity, compatibility, magnetism, and
surface activity (Camargo et al. 2009). Nanocomposites are used in catalysts,
sensors, opto-electronic devices, magnetic devices, food packaging, fuel cells,
dentistry, construction, coating, medicine, and automobiles (Okpala 2014). Nano-
composites also found potential applications in the separation of heavy metal ions.
The prospective of nanocomposites over the separation of actinides has emerged
recent times.
CNT nanocomposite was prepared by using hydroxylated fullerene (C60(OH)n),
carboxylated fullerene (C60(C(COOH)2)n), and oxidized-MWCNTs (Wang et al.
2013). The presence of hydroxylated fullerene (C60(OH)n) and carboxylated fuller-
ene (C60(C(COOH)2)n) in MWCNTs increased the sorption of Th4+ onto oxidized
MWNCTs at pH < 4. However, the sorption of Th4+ lowered at pH > 4 with the
increasing concentration of C60(OH)n or C60(C(COOH)2)n (Wang et al. 2013). This
striking behavior was due to the good sorption affinity of C60(OH)n or C60(C
(COOH)2)n onto oxidized MWCNTs by strong π–π electron donor–acceptor inter-
actions between the flat surfaces of both aromatic C60(OH)n/C60(C(COOH)2)n and
oxidized MWCNTs. Thus, the increasing concentration of fullerene created a com-
petitive pathway for the sorption of Th4+. Polyvinyl alcohol MWCNT
(PVA-MWCNT) composite was evaluated for the removal of U(VI) (Abdeen and
Akl 2015). The maximum sorption of U(VI) on PVA-MWCNTs was observed at
pH 3 and the adsorbed uranium could be desorbed by using 0.1 M EDTA.
Various GO-based composites were synthesized and used for environmental
remediation. GO-supported sepiolite (GO@sepiolite) composites were synthesized
applied for the removal of U(VI) (Cheng et al. 2013a). GO-activated carbon felt
(GO–ACF) composites were prepared by an electrophoretic deposition and subse-
quent thermal annealing(Chen et al. 2013b). GO–ACF showed high sorption capac-
ity for U(VI) due to presence of carboxyl functional groups in GO–ACF.
The sorption of U(VI) on GO-supported polyaniline (PANI@GO) nano-
composites was investigated. The PANI has a strong affinity for radionuclides and
heavy metal ions due to the large number of amine and imine functional groups;
these functional groups can form very strong complexes with radionuclides on the
nanocomposite surfaces (Sun et al. 2013). The chemical binding of radionuclides
with the nitrogen-containing functional groups is much stronger than that of radio-
nuclides with the oxygen-containing functional groups. The sorption of U(VI) ions
on GO-polypyrrole (GO/PPy) composites was much higher than that of U(VI) on
either GO or PPy in an aqueous system (Hu et al. 2014). The highly selective
sorption capacity towards U(VI) was observed due to the strong coordination
between the U(VI) ions and nitrogen donor atoms on the GO/PPy composites.
GO/PPy composites could be regenerated and reused. Hierarchical three-
dimensional composite (layered double hydroxide/graphene) was obtained via in
situ growth of layered double-hydroxide (LDH) nanosheet arrays onto graphene
sheets and sorption of U(VI) was performed from aqueous media (Tan et al. 2015c).
Poly(amidoxime)-reduced GO (PAO/RGO) composites synthesized by in situ poly-
merization showed excellent sorption capability for U(VI) (Chen et al. 2014).
The sorption capacity of PAO/RGO composites for U(VI) showed highest sorption
capacity (872 mg g 1) compared to other GO-based composites.
Magnetic Nanocomposites
Even though nanomaterials possess extraordinary features, it is practically compli-

cated to remove the suspended nanoparticles from the solution. This problem can be
tackled by introducing magnetic nanocomposites that can be easily removed by the
application of magnetic field. Design of chelator-tethered magnetic nanomaterials
revolutionized the process of separation of metal ions. They work on the simple
principle of magnetism but they are versatile with high efficiency in the separation.
The main advantage of using magnetic materials is the easy separation of the sorbent
from the solution after the extraction of metal ions (Teja and Koh 2009).
The MWCNT nanocomposites were prepared by incorporation of Fe2O3 or
CoFe2O4 magnetic particle. These magnetic Fe2O3-MWCNT (Liu et al. 2014) and
CoFe2O4-MWCNT (Tan et al. 2015a) composite were evaluated for the sorption of
Th(IV) and U(VI) radionuclides, respectively. The removal of U(VI) using nano-
scale zero-valent iron (nZVI) and reduced graphene oxide-supported nanoscale zero-
valent iron (nZVI/RGO) was studied (Sun et al. 2014). The U(VI) species such as
UO2 2+, UO2OH+, and (UO2)3(OH)5+) were efficiently removed in the weak aqueous
acid medium. GOs have high dispersion properties in aqueous solution due to their
hydrophilic nature; thereby it is difficult to separate GOs from aqueous solution by
using the traditional separation techniques after the GOs are applied as adsorbents in
the sorption process. The magnetic Fe3O4/GO composite was prepared from natural
flake graphite and employed as adsorbent to remove U(VI) ions (Zong et al. 2013).
After U(VI) sorption, magnetic Fe3O4/GO composite was easily removed from
aqueous solution due to magnetic separation. Amidoximated magnetite/ GO
(AOMGO) composites were also synthesized and applied to U(VI) sorption, and
had a more sorption capacity compared to Fe3O4/GO composite (Zhao et al. 2013).
MnO2–Fe3O4–RGO was successful for the removal of U(VI) (Tan et al. 2015d). In
addition, U(VI)-loaded MnO2–Fe3O4–RGO was efficiently regenerated and reused.
The CoFe2O4-reduced graphene oxide nanocomposite was used for the extraction of
uranium (Tan et al. 2015b). The superparamagnetic GO-Fe3O4 nanocomposite was
synthesized and evaluated for the uptake of Am3+, UO22+, Th4+, and Pu4+ in mildly
acidic solutions (Gadly et al. 2017). The uptake of tetravalent metal ion reduced with
increase in hydrolysis due to the reduction in the effective nuclear charge. These
composites are recyclable and therefore can be reused. Magnetic ferberite-GO
nanocomposite was utilized for the extraction of U(VI) from aqueous solution
(El-Maghrabi et al. 2017). This composite possesses high recycling capacity and
the morphology remained unaltered after several stages of reuse.
Fe3O4-encapsulated ZIF-8 nanocomposite was used for the separation of U(VI)
from Ln(III) under various experimental conditions (Min et al. 2017). The fast
kinetics and high U(VI) uptake capacity were observed for this kind of metal organic
framework composite. Attapulgite-Fe2O3 nanocomposites prepared by chemical
route were used for the separation of U(VI) from its aqueous solution (Chen et al.
2013). At higher pH, sorption of U(VI) occurs through inner sphere surface com-
plexation and at low pH sorption of U(VI) follows outer-sphere surface
complexation.
Mesoporous Materials for Sorption
Besides nanomaterials, mesoporous materials such as activated carbon (Carboni

et al. 2013), silica (Vivero-Escoto et al. 2013), and polymeric membrane with pore
size in the range of nano dimensions (size between 2 and 100 nm) also gained
prominence in the separation of actinides. Ordered mesoporous carbon and silica
materials (MCM-Mobil Composition of Matter-41,48 and SBA-15-Santa Barbara
Amorphous-15) are novel families of the fascinating porous solids, which have the
advantages of large surface area, well-defined pore size, excellent mechanical
resistance, non-swelling, exceptional chemical stability and radiation tolerance, as
well as extraordinarily wide possibilities of functionalization (Darmstadt et al. 2003;
Lee et al. 2011). These advantages make the ordered mesoporous carbon and silica
compounds attractive for nuclear waste disposal.
The U(VI) was entrapped using MCM-41 and MCM-48 molecular sieves based on
direct template ion exchange (Vidya et al. 2001, 2004). It was found that the entrapment
of U(VI) was facilitated by the large pore size and the high surfactant content in the
as-synthesized host materials. However, these sorbents normally show poor selectivity
and slow sorption kinetics for U(VI). To promote the sorption selectivity, and achieve
higher sorption capacity and faster sorption kinetics, functionalized mesoporous mate-
rials were synthesized. 4-Acetophenone oxime-functionalized ordered mesoporous
carbon CMK-5 (Oxime-CMK-5) was developed for U(VI) sorption (Li et al. 2011).
The U(VI) sorption by Oxime-CMK-5 was found to be rapid and pH dependent
(Fryxell et al. 2005; Lin et al. 2005). It was found that the composite can be reused
without considerable loss in sorption capacity. The 5-nitro-2-furaldehyde-modified
mesoporous silica (MCM-41) was used for extraction of U(VI) (Yousefi et al. 2009).
The sorbent exhibits good stability, reusability, high sorption capacity, and fast rate of
equilibrium for sorption/desorption of U(VI). Recently, the phosphonate-
functionalized MCM-41(NP10) (Yuan et al. 2011) and amino-functionalized SBA-15
(APSS) (Liu et al. 2012) were synthesized by co-condensation and grafting method,
respectively. These synthesized materials were used as sorbents for the removal of U
(VI) from aqueous solution. These new sorbents offered large sorption capacity and
possess ultrafast sorption kinetics. Furthermore, these silica materials show a desirable
selectivity for U(VI) ions over a wide range of competing metal ions.
Ordered mesoporous carbon (OMC) was synthesized and investigated for the
sorption and desorption of Pu(VI) and Eu(III) (Parsons-Moss et al. 2014). Extraction
of uranium in aqueous media by nanocomposite of two-dimensional layered double
hydroxide with silica nanoparticles revealed that sorption of U(VI) is through inner-
sphere surface complexation and electrostatic interaction (Yang et al. 2017a).
Layered double-hydroxide carbon dot composite was used for the extraction of
U(VI) and Am(III) from aqueous solutions (Yao et al. 2018). The dispersion of
carbon dots into layered double hydroxides prevents agglomeration of carbon dots
and thereby increased surface area and extraction efficiency of actinides.
Self-assembled monolayer on mesoporous support (SAMMS) was prepared by
assembling monolayers of molecules in the mesoporous support and functionalizing
the free end of the monolayers (Fryxell et al. 1999). The large surface area of these
functionalized mesoporous materials provides more active sites for the adsorption of
metal ions. Moreover, the high porosity enhances the diffusion of metal ions and
sorption kinetics. This kind of ceramic support is stable under extreme acidic,
corrosive, and oxidizing environment. Glycinyl-urea-, carboxylate-, and
phosphonate-functionalized SAMMS were investigated for the extraction of U
(VI), Pu(IV), and Am(III) from aqueous solutions containing several foreign metal
ions (Fryxell et al. 2005). Isomers of hydroxypyridinone-functionalized SAMMS
were investigated to understand the extraction behavior of Pu(IV), Np(V), and U
(VI) (Lin et al. 2005). The multiple ligand–metal interactions and intramolecular
hydrogen bonding enhanced the extraction of actinides.
The surface ion-imprinted mesoporous silica was investigated for the separation
of U(VI) from highly acidic solutions (Yang et al. 2017b). The sorbent was synthe-
sized using U(VI) (uranyl) as the template and diethylphosphatoethyltriethoxysilane
as functional group. The surface ion-imprinted mesoporous silica have nano-sized
three-dimensional cavity that is specific for U(VI). Using this sorbent the fast
kinetics and higher selectivity for U(VI) were observed when compared to non-
ion-imprinted similar mesoporous materials. The material is also resistant to radia-
tion such that the performance did not deteriorate after five consecutive usages of the
ion-imprinted polymer.
Mesoporous Membrane for Sorption
Removal of radionuclides from aqueous waste by membrane separation using nano-

filtration (NF)/reverse osmosis (RO)/ultrafiltration (UF) membrane has become one
of the emerging technologies with a rapid growth. It has drawn the attention of
researchers in the field of separation technology with its better performance compared
to conventional separation processes. In these filtration methods, the feed mixture is
pressurized to pass through nano/micro-sized pores of the membrane and then
separated into a retentate (part of the feed that does not pass through the membrane)
and a permeate (part of the feed that passes through the membrane). During this
process, the actinides are concentrated in the retentate by sieving and adsorption.
Reverse Osmosis (RO)
Reverse osmosis (RO) can effectively remove nearly all inorganic contaminants
from water. RO process was applied for the treatment of effluents containing
uranium. In this process, uranium content in permeate is reduced to less than
1 mg L1, where the removal of uranium is 99.5% (Hsiue et al. 1989; Prabhakar
et al. 1992). RO process was conducted to remove uranium, technetium, tritium,
strontium, and cesium from liquid effluents and groundwater (Garrett 1990; Gamal
Khedr 2013). It was demonstrated that all of the above contaminants could be
removed to less than the regulated limits, except tritium. Recently, RO was used in
the framework of the Fukushima-Daiichi accident to treat contaminated seawater
(Fournel et al. 2012).
Nanofiltration (NF)
Nanofiltration membranes have a nominal pore size of approximately 0.001 microns

and a molecular weight cutoff (MWCO) of 200–1000 daltons (Da) (Yong Du et al.
2016). NF membranes are very commendable for retention of multivalent cations
and organic solutes. NF membranes are generally manufactured from cellulose
acetate or polyamide materials. The polyamide-based NF membrane was used for
treatment of radioactive effluents containing specific activity levels in 10 kBq/L. It
was observed that the level of radioactive contaminants could be reduced from
10 kBq /L to few Bq/L. Studies on selective removal of uranium from aqueous
solution using nanofiltration membranes showed relatively high selectivity, despite
the high concentration of other divalent and monovalent cations (Reguillon et al.
2008; Raff and Wilken 1999).
Ultrafiltration (UF) Combined with Sorption/Precipitation/

Complexation
Ultrafiltration has a pore size of approximately 0.002–0.1 microns, an MWCO of

approximately 10,000–100,000 daltons. UF membranes are constructed from a wide
variety of materials, including cellulose acetate, polyvinylidene fluoride, polyacry-
lonitrile, polypropylene, polysulfone, polyethersulfone, or other polymers. Each of
these materials has different properties with respect to the surface charge, degree of
hydrophobicity, strength, flexibility, pH, and oxidant tolerance. UF membranes have
large pore size than NF membrane and they are not effective in retaining radioactive
metal ions. Hence, in order to retain the radioactive ions, size enhancement of
radioactive species by means of sorption/precipitation/complexation is done prior
to UF. UF experiment was conducted with 239,240Pu and pseudo-colloids of Fe in
water having dissolved organic carbon (DOC) in the range of 10–60 mg/L. The
presence of DOC increases the colloidal size of Fe and acts as a matrix for high
sorption of plutonium (Singhal et al. 2009). Studies on ferric hydroxide precipitation
employed for the treatment of low-level waste (LLW) containing 241Am showed
>99.9% removal of 241Am (Gao et al. 2004). The recovery of 241Am was also
accomplished using sodium dodecyl sulfate (SDS) micellar solution at pH > 3
(Kedari et al. 2009).
Nanopolymer/Dendrimer-Assisted Ultrafiltration
Polymer-assisted ultrafiltration (PAUF) is a technology under development for

selective concentration and recovery of valuable metal ions from wastewater.
PAUF is a combination of ion exchange or chelating property of a functionalized
water-soluble polymer and sieving power of an ultrafiltration membrane. As the
molecular weight of metal polymer complex is larger than the molecular weight
cutoff of the membrane, they are concentrated in the retentate and permeate is free
from metal ions. The polymers could be regenerated by changing pH of the solution.
With the recent significant advantages in nanoscience and nanotechnology, var-
ious nanostructured polymers/dendrimers were devised for a wide range of advanced
applications. Examples include the use of polymer nanoparticles as drug delivery
devices, polymer nanofibers as conducting wires, and polymer thin film as optoelec-
tronic devices. Like most other nanomaterials, nanostructured polymers also possess
interesting mechanical, electronic, optical, and even magnetic properties that are
different from those of the bulk materials, depending on their size, shape, and
composition.
Dendrimers are a new class of polymeric nanomaterials (after linear, cross-linked,
and branched polymers) having unique properties such as high degree of branching
unit, high density of surface functional group, and narrow molecular weight distri-
bution. They are spheroid or globular nanostructures that are precisely engineered to
carry molecule encapsulated in their interior void space or attached to the surface.
Size, shape, and reactivity are determined by generation (shell) and chemical
composition of the core, interior branching, and surface functionalities. Dendrimers
are constructed through a set of repeating chemical synthesis procedures that build
up from the molecular level to the nanoscale region under conditions that are easily
performed in a standard organic chemistry laboratory. The dendrimer diameter
increases linearly whereas the number of surface groups increases geometrically.
Dendrimers are very uniform with extremely low polydispersities, and are com-
monly created with dimensions incrementally grown in approximately nanometer
steps from 1 to over 10 nm. The control over size, shape, and surface functionality
makes dendrimers one of the “smartest” or customizable nanotechnologies commer-
cially available (Tomalia et al. 1985). Figure 9 provides a schematic of a generalized
dendrimer structure.
Among the uses of dendrimer the important one is that they can be used to
selectively bind to, or react with, a particular element, ion, or molecule of choice.
They are very large, yet soluble, macroligands, and well-defined sizes and shapes
can be made, with hundreds or even thousands of complexing sites and reactive
chain ends. They can also be covalently linked to each other or to other macromol-
ecules to form supramolecular assemblies of various size, shape, and topologies.
Dendritic macromolecules can also be functionalized with surface group that make
them soluble in selected solvents or bind to selected surface (Diallo et al. 2009).
Currently, dendrimers are under investigation as metal-sequestering agents for waste
remediation technologies (Diallo 2006). The highly branched molecules with numer-
ous functional groups can be formulated to provide the required properties of water
Fig. 9 Schematic of a generalized 2D and 3D view of dendrimer structure (Kukowska-Latallo

et al. 1996)
solubility, selectivity, high loading capacity, and so on. The use of poly(amido)amine
(PAMAM) and poly(propylene)imine (PPI) dendrimers and their derivatives in
combination with ultrafiltration technique have shown potential applications in
removal of metal ions such as Cu(II), Ni(II), Co(II), Pd(II), Pt(II), Zn(II), Fe(III),
Ag(I), Au(I), and U(VI) from dilute aqueous solution (Rether and Schuster 2003;
Diallo et al. 2008; Arkas et al. 2003).
Removal of U(VI) and Th(IV) ions from aqueous solution by ultrafiltration
(UF) and dendrimer-assisted ultrafiltration (DAUF) was investigated (Ilaiyaraja
et al. 2014). Regenerated cellulose acetate ultrafiltration membrane was used during
ultrafiltration and PAMAM dendrimer chelating agent used as a complexing agent in
DAUF. In UF process, removal of U(VI) and Th(IV) metal ions is observed to be
based on adsorption/mass deposition on membrane. PAMAM dendrimer contains a
large number of nitrogen and oxygen atoms as amino and amide groups on branches
and terminal surface showing strong chelating action towards actinides. In DAUF,
the water-soluble PAMAM dendrimer effectively forms complex with hydrolyzed U
(VI) and Th(IV) species in aqueous solution and gets concentrated in the retentate. In
both UF and PAMAM-DAUF, the U(VI) and Th(IV) were more than 95% in the
weakly acid medium (pH 5–6). However, in UF, the membrane fouling (plugging of
membrane pores) was observed on repeated use. PAMAM-DAUF was shown to be
effective in the removal of U(VI) and Th(IV) at pH > 4.
Conclusion
Separation of radionuclides from aqueous streams is currently one of the most

significant and challenging problems. The main challenge involved is the separation
of various long-lived actinide species that exist simultaneously in aqueous streams
and their effective separation in the presence of a large excess of competing ionic
species. Therefore, materials to be used for separation of actinides species are

required to be more efficient and specific enough. This chapter revealed the fact
that there has been a large increase in utilization of nanomaterials over the last few
decades. All above-mentioned studies have dealt with separation of radionuclides
using nanomaterials. These studies emphasize that nanomaterials show several
interesting aspects for application in nuclear waste disposal and environmental
remediation. Due to nanostructural and surface features, there is a tendency for
various interactions (hydrophobic, dipole, π–π interactions, formation of hydrogen
and other bonds), good sorption capacity, kinetic properties, and thermal and
chemical stabilities. Moreover, their modified or functionalized forms are promising
candidates for specific actinide separation. The magnetic nanoparticles are incorpo-
rated into sorbent to facilitate the easy removal of suspended sorbent from aqueous
solution after the extraction of metal ions. This approach promises industrial level
scaling up of separation process. However, some nanomaterials are not quite stable
under the conditions of ionizing radiation and cannot perform for relatively longer
period of time in complex chemical environments. Furthermore, the issues on
hazardous nature of nanomaterials itself to environment also need to be evaluated
and clarified. The dendrimer-assisted ultrafiltration possesses potential application in
decontamination of radioactive wastes. However, the synthesis of dendrimer
involves a number of steps that are time consuming and expensive. Hence, attention
shall be provided for reducing the number of steps involved in dendrimer synthesis.
In these regards, full realization of a true potential of nanomaterials for radionuclide
separation requires further studies concentrating on developing highly efficient,
selective, radiation-resistant, renewable, economic, and environment-friendly nano-
materials. Therefore this chapter provides a deeper insight into speciation and
separation of actinide species in aqueous stream.
Cross-References
▶ Advanced Treatment Technologies

▶ Environmental Treatment Technologies: Adsorption
▶ Nanomembranes for Environment
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Part V
Management of Special Wastes: CO2, CH4,
NOX, SO2, Carbon Particles, and Oil Spills
Prospects and Issues of Phosphorus
Recovery as Struvite from Waste Streams 32
Sampriti Kataki and D. C. Baruah
Contents
Phosphorus: Role, Issues, and Possibilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 822
P Recovery as Struvite: An Alternative P Fertilizer and Factors Affecting . . . . . . . . . . . . . . . . . . . 824
Struvite: As Nuisance and Issues Concerning Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825
Benefits Incurred from Struvite Recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
Potential Sources for Recovery of Struvite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 827
Commercial Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 834
Effects of Nonparticipating Ions on Crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 841
Technology Enhancement Through Process Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 842
Methods of Struvite Recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 842
Chemical Precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
Electrochemical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
Ion Exchange Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
Microbial Biomineralization Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
Use of Different Pretreatments for Maximizing Struvite Recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
pH Modification Using Acid/Base Leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
Chelating Agent Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
Microwave Heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
Enhanced Biological Phosphorus Removal (EBPR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 850
Use of Seed in Struvite Crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 850
Alternative Magnesium Sources for Struvite Precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 852
S. Kataki (*)
Energy Conservation Laboratory, Department of Energy, Tezpur University, Tezpur, Assam, India
e-mail: sam_kat@tezu.ernet.in
D. C. Baruah
Energy Conservation Laboratory, Department of Energy, Tezpur University, Tezpur, Assam, India
Department of Mechanical and Industrial Engineering, University of South Africa, Pretoria,
South Africa

https://doi.org/10.1007/978-3-319-73645-7_19
822 S. Kataki and D. C. Baruah
Application of Struvite as Soil Fertilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854

Fertilizer Properties of Struvite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
Effect of Struvite Application on Crop . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 858
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 859
Abstract
Finite resources of non-substitutable plant nutrient like phosphorus (P) make
recovery of it an attractive option of renewed interest from alternative waste
sources. In this context, feasibility of struvite recovery (MgNH4PO4. 6H2O), an
alternative P fertilizer, is already established from different waste streams with
reasonably high ortho-P recovery efficiency (~90%). Feasibility of struvite recov-
ery has been established at laboratory scale for a range of sources of farm,
municipal, and industrial origin. Municipal wastewater is the most common
struvite recovery source, whereas farm wastes represent easily accessible stock
with reliable availability. Depending on the source characteristics, the recovery of
struvite may require some process modifications such as addition of P and NH4+
salt and incorporation of pretreatments. However, except for municipal sludge
and urine, development of cost-effective, targeted, and environmentally friendly
full-scale recovery of struvite is limited due to inherently heterogeneous nature of
the sources and unfavorable economics. In recent years, an increasing research
concern can be seen toward the techno-economical aspects of the process for
development of competent and energy-efficient process from alternative potential
struvite sources with incorporation of more efficient method, Mg source, and seed
material. Studies on struvite’s application aspect identify its favorable impact on
crop though with variation attributed to soil type, plant type, and climate;
however, its field-scale long-term impact, its applicability within regulatory limits
of fertilizer, and users’ perception remain other concerns. Nevertheless, consid-
ering the related benefits of recovery process, struvite recovery appears to be an
attractive and feasible pathway provided uncertain aspects are addressed through
appropriate research and development.
Keywords
Struvite · Phosphorus · Phosphate · Recovery · Seed · Magnesium · Fertilizer ·
Nutrients · Pretreatments · Anaerobic digestion · Agriculture · Farm waste ·
Industrial waste · Municipal waste · Ammonium · Calcium
Phosphorus: Role, Issues, and Possibilities
Currently, agricultural lands occupy 40% of global land and contribute 4% to the
global GDP, making agriculture as one of the most important enterprises in the world
(Warnars and Oppenoorth 2014). In recent years, agricultural growth has gained new
significance and dimension, as appropriate intensification of agricultural sector is of
32 Prospects and Issues of Phosphorus Recovery as Struvite from Waste Streams 823
vital importance to ensure food security for growing population. Fertilizer sector
constitutes the backbone of agricultural intensification. In long-term conventional
cultivation practices, substantial amount of plant essential nutrients is removed
through crop. It is not possible for soil to meet crop nutrient requirement without
external supplementation of proper nutrient inputs. Thus fertilizer has been and will
continue to be one prime input in global agriculture to achieve self-sufficiency in
food grain production. Currently, an average of 40–60% of the world’s food pro-
duction is attributable to fertilizer inputs (Roberts 2009). Phosphorus (P) is one such
non-substitutable fertilizer, and agroecosystems account for 80–90% of the world’s
total P consumption (Childers et al. 2011). Current global P demand is forecast to
grow at an annual rate of 1.9% over the period 2013–2018 with a more stabilized
consumption in the developed countries, but demand is seen increasing in the
developing world (Heffer and Prud’homme 2010, 2014) (Fig. 1).
Presently the only source of commercial P fertilizer is natural phosphate rock
(both sedimentary and igneous) with no known chemical or technological substitute.
Rock P reserve is mostly spread in limited number of countries, viz., China, the
USA, Morocco, and Russia, contributing 75% of world total production (Childers
et al. 2011; Heckenmüller et al. 2014). However, there are some uncertainties
associated with the actual extent of commercially viable global phosphate stock
(Vaccari 2009). Further, increasing population, uncertain backup of global stock, and
progressive global P consumption are expected to put more pressure on dwindling
accessible P supplies. P appears as a key limiting nutrient in 40% of the world’s
arable soils due to its slow diffusion and high fixation with other chemical constit-
uents (Ca, Fe, Al, Mg, K) that becomes available through chemical weathering
25
20
Phosphorus(Mt)
15
10
0
1960 1964 1966 1972 1976 1980 1984 1988 1992 1996 2000 2004 2008 2012 2016
Year
Developing countries Developed countries World forecast
Fig. 1 Global phosphorus fertilizer consumption (Adapted from Heffer and Prud’homme 2010)
Fig. 2 Issues favoring phosphorus recovery
(Shen et al. 2001; Vance 2001). All these issues (Fig. 2) argue in favor of recovery of
P with the help of cost-effective, energy-efficient, and environmentally compatible
means from non-conventional P-rich sources to produce products with enhanced
nutrient values competitive with mineral fertilizers. P recovery technologies are
based on the principle of fixation of P through biological method or chemical
precipitation by metal salts (Le Corre et al. 2009).
P Recovery as Struvite: An Alternative P Fertilizer and Factors

Affecting
The most common method of P recovery is through production of mineral or salt

precipitates from P-rich sources. Struvite or magnesium ammonium phosphate
(MAP/MgNH4PO4˙6H2O) is such P-rich mineral which is by mass 44% crystal
water, 39% phosphate, 10% magnesium and 7% ammonium (Gell et al. 2011).
Precipitation of struvite needs the presence of three ionic species, magnesium
(Mg2+), ammonium (NH4+), and orthophosphate (PO43) in an alkaline solution in
equimolar (1:1:1) concentrations (Rahaman et al. 2008). pH, ionic strength of
participating molecules, the presence of impurities or nonparticipating ions, mixing
energy, residence time for crystallization, and the type of crystallization reactor are
the factors that govern the precipitation of struvite in P-rich sources (Doyle and
Parson 2002; Nelson et al. 2003; Le Corre et al. 2007; Koralewska et al. 2009;
Hutnik et al. 2011) (Fig. 3). The basic chemical reaction to form struvite can be
expressed using Eq. 1. It was estimated that globally 0.63 million tons of P per year
could be generated as struvite from the wastewater treatment plants, which would be
sufficient to reduce phosphate rock mining by 1.6% (Shu et al. 2006).
Fig. 3 Defining factors

affecting struvite precipitation
Mg2þ þ PO4 3 þ NH4 þ þ 6H2 O , MgNH4 PO4 6H2 O # pKs

¼ 12:6 25 C (1)
(Li et al. 1999)

pH is considered to be one of the most significant factors of struvite precipita-
tion as solubility of struvite is highly pH dependent. Minimum solubility of
struvite is found within the pH range of 8–11, and struvite solubility decreases
with increase in pH (Ohlinger et al. 1998). At constant pH, higher ionic strength or
supersaturation of participating ions is reported to induce nucleation rate posi-
tively, reducing induction time (Bouropoulos and Koutsoukos 2000). Mixing
energy is another controlling factor for crystal growth, increase of which reduces
induction period, when supersaturation is constant (Ohlinger et al. 1999; Bhuiyan
et al. 2007). On the other hand, the presence of foreign ions can inhibit formation
of struvite by competing with struvite-forming participating molecules and can
decrease purity of recovered struvite by coprecipitation (Jones 2002; Le Corre
et al. 2005).
Struvite: As Nuisance and Issues Concerning Prevention
Struvite formation appears as a physical nuisance mostly in wastewater treatment

plants (in pipes, heat exchangers) where it occurs spontaneously when appropriate
conditions of molar ratio of Mg2+, NH4+, and PO43, pH, and mixing energy are
achieved (Bhuiyan et al. 2007). In wastewater plants, areas most affected by
struvite scale formation are anaerobic digester units, digester liquor discharge
line, heat exchangers, and centrifuge dewatering units downstream of the digester
system. During anaerobic digestion of wastewater sludges, NH4+ is released from
degradation of nitrogenous material in organic wastes creating suitable conditions
for struvite formation (Al-Seadi and Lukehurst 2012; Bhuiyan et al. 2007). Areas
of a wastewater treatment where there is an increase in turbulence (pumps,
aerators, and pipe bends) are more prone to struvite scale formation as aeration
helps to increase pH by stripping off CO2 (Borgerding 1972). Thus, overall system
Fig. 4 Struvite control methods and limitations associated
efficiency and operational costs are affected due to struvite scaling (Doyle and
Parsons 2002; Jaffer et al. 2002; Petzet and Cornel 2011).
There are some control measures employed to control formation of struvite as
shown in Fig. 4. However, none of the methods are completely affective to
alleviate the problem and are associated with drawbacks, viz., cost affectivity in
terms of labor and materials and time, increase in total sold content, non-suitability
of sludge disposal, difficulty in P recovery from Fe/Al salt (Ohlinger et al. 1998;
Wu et al. 2005), concern about agricultural application of remaining sludge
(Wu et al. 2005), and multiple factor-dependent affectivity (Wu et al. 2005)
(Fig. 4). Therefore, failing to achieve at an working mitigation strategy to deal
with the problem, a controlled, designed, and intentional struvite precipitation has
been attempted leading to consideration of “struvite production” a resource recov-
ery method.
Benefits Incurred from Struvite Recovery
Struvite recovery, as a method of nutrient recycling, has expansive multifaceted

benefits and is receiving support from R&D. The recovery process of struvite can
create multiple benefits directly or indirectly as shown in Fig. 5. Apart from
development of a product with enriched value, P recovery process also adds to
some associated benefits in terms of environmental quality improvement of
P-rich source, increase in dry matter content, volume reduction of waste handled
and supplementation to chemical fertilizer, closing of open P cycle, and enhanc-
ing performance efficiency of waste treatment facilities (Woods et al. 1999;
Shu et al. 2006; Gell et al. 2011; Estevez et al. 2014). Integration of nutrient
recovery with waste management is expected to result in cost-effective
relocation of excess nutrients from otherwise polluting effluents (Burns and
Moody 2002).
Fig. 5 Benefits derived from struvite recovery technology
Potential Sources for Recovery of Struvite
The biogeochemical cycle of P is an open cycle. It has been reported that only 15%
of the total P extracted from mines and used for food production is eventually
consumed by humans, whereas remaining P is lost to the environment (Roy et al.
2006; Suh and Yee 2011). During crop cultivation and livestock, meat, and dairy
production, more than 66% of the total P extracted is lost, and remaining 19% is lost
through household food waste, mining waste, and fertilizer manufacturing waste
(Karunanithi et al. 2015). Thus, during the cycling of P in the terrestrial and aquatic
environment, the lost P ends up in some easily accessible and abundant natural
sources (Atkinson et al. 2010). Therefore, a sustainable approach for effective P
management is recycling back of P from various identified P-rich sources. To
identify such sources, composition of source, abundance, and need for their man-
agement or treatment remain the main driving forces. In literature a range of waste
sources has been investigated to understand the feasibility struvite recovery.
Depending upon their occurrence or origin, these sources can be categorized into
three groups, viz., farm waste, industrial waste, and municipal waste. Various
waste sources of farm, industrial, and municipal origin reported in literature are
shown in Tables 1, 2, and 3 along with waste characteristics and process conditions.
Farm wastes: Manures are rich in P and NH4+, which is favorable for struvite
recovery. It has been reported that more than 70% of consumed animal feed is
excreted as urine and feces which contain organic matter, N, P, K, and other
micronutrients (Barnett 1994). Thus manures represent inexpensive and most abun-
dantly available sources for recovery of struvite, and struvite recovery could serve as
828
Table 1 Potential sources of struvite recovery of farm origin (Adapted from Kataki et al. 2016a with modification)
PO4-P NH4-N P NH4+
Sources (mg L1) (mg L1) Mg source Additional chemical pH recovery (%) recovery (%) Reference
Poultry 572 NR MgCl2 – 9 91 NR Burns et al. (2001)
manure NR 1318 MgO, MgSO4, NaHPO4, KH2PO4, 9 NR 85 Yetilmezsoy and Sapci-
MgCl2 H3PO4 Zengin (2009)
Dairy NR 255–519 MgCl2, Mg Na2HPO4 8.5–9.2 NR 95 Demirer et al. (2005)
manure (OH)2
NR NR MgCl2 – 8.5 82% NR Zhao et al. (2010)
19 1405 MgCl2 – 7.2 69 NR Shen et al. (2011)
Cattle NR 7732 Brine – 9 NR NR Prabhu and Mutnuri (2014)
urine
Swine 72 532 Bittern – 7.5–8.5 73 NR Suzuki et al. (2007)
manure 42 234 MgCl2 KH2PO4 9 89 70 Perera et al. (2007)
30–56 732–931 MgCl2 KH2PO4 9 97 90 Ryu and Lee (2010)
161 985 Struvite H3PO4 8–8.5 96 80 Huang et al. (2011a, b)
pyrolysate
55–139 1013–1426 MgCl2 Na3PO4 10 99 87 Zhang et al. (2012)
Swine 3000 mg kg1 1900 mg kg1 MgCl2 H3PO4 7.3 NR NR Fukumoto et al. (2011)
compost DM DM
NR not reported, DM dry matter
S. Kataki and D. C. Baruah
32
Table 2 Potential sources of struvite recovery of industrial origin (Adapted from Kataki et al. 2016a with modification)
Total P/PO4- TN/NH4-N Additional NH4+
Sources P (mg L1) (mg L1) Mg source chemical pH P recovery (%) recovery (%) Reference
Leather tanning 2.5–8 119–1076 MgCl2 Na2HPO4 9 NR 89 Tunay and
wastewater Kabdasli
(2001)
Textile industry NR 20–368 MgCl2 KH2PO4 8–9.5 NR 84 Kabdasli et al.
wastewater (2000)
Abattoir wastewater/ 5.5–10 83–208 MgCl2 Na2HPO4 9 NR 78 Tunay and
meat packing effluent Kabdasli
(2001)
6 210–220 MgCl2 NaH2PO4 9.5 NR 89.5 Kabdasli et al.
(2009)
Carmine dye wastewater 3490 2320 MgO Na2HPO4 8.5–9 100 89 Chimenos
et al. (2003)
AD effluent of molasses- 24 1400 MgCl2 – 8–9 NR 78–95 Türker and
based wastewater Celen (2007)
Semiconductor 286 100 MgCl2 – 9 70 98 Kim et al.
wastewater (2009)
Anaerobic effluent from 43–127 208–426 MgCl2 – 8.5–8.7 19–89 NR Moerman et al.
potato processing (2009)
Coking/coke oven NR 520 MgCl2 Na2HPO4 9.5 NR 84 Zhang et al.
wastewater (2009)
56 3500 MgCl2 Na2HPO4, Ca 9–9.5 NR 95 Kumar and Pal
(H2PO) (2013)
Prospects and Issues of Phosphorus Recovery as Struvite from Waste Streams
Rare-earth wastewater NR 4535 Brucite H3PO4 8.5–9.5 97 95 Huang et al.

(2011a, b)
(continued)
829
830
Table 2 (continued)
Total P/PO4- TN/NH4-N Additional NH4+
Sources P (mg L1) (mg L1) Mg source chemical pH P recovery (%) recovery (%) Reference
Nylon wastewater NR 550 Brucite, H3PO4, 8.5 94 88 Huang et al.
MgSO4 Na2HPO4 (2012)
7Aminocephalosporanic 36 1128 MgCl2, H3PO4, 9 NR 74% Li et al. (2012)
acid wastewater MgO, Na3PO4,
MgSO4 NaH2PO4
Fertilizers industry NR 1197 Struvite – 9.5 NR 97 Yu et al.
wastewater pyrolysate (2012)
4.45% NR MgCl2 NH4Cl 9–11 99.5 NR Matynia et al.
(2013)
Cola beverage 415 NR MgCl2 NH4Cl 9.5 97 NR Foletto et al.
(2013)
Yeast industry 17.4 161 MgCl2 Na2HPO4 9.5 83 81 Khai and Tang
(2012)
Wastewater 10.8 528 MgSO4 H3PO4 9 NR 87.55 Uysal and
Demir (2013)
32
Table 3 Potential sources of struvite recovery of municipal origin (Adapted from Kataki et al. 2016a with modification)
Total P/PO4-P TN/NH4-N NH4+
Sources (mg L1) (mg L1) Mg source Additional chemical pH P Recovery (%) recovery (%) Reference
Human urine 240 6963 MgCl2 – 9 96 NR Ronteltap et al.
(2007)
460 40 MgO, MgCl2 – 9.4 95 NR Wilsenach et al.
(2007)
206 NR/7220 MgCl2 Na2HPO4 8–11 85 95 Liu et al. (2008b)
NR NR MgO – 9.2–9.5 95–100 50 Ganrot et al. (2007)
197 2540 Mg anode – 8.9 84 NR Hug and Udert
(2013)
156–194 3200–4990 MgO – 9.1–9.3 95 NR Morales et al. (2013)
416 245 MgO, MgCl2 – 9 92 90 Latifian et al. (2013)
Landfill NR 2750–2900 MgCl2,MgO, Na2HPO4, Ca 9 92 NR Li and Zhao (2003)
leachate MgSO4 (H2PO), H3PO4
10.5 1795 MgCl2 KH2PO4 9 99 87 Kim et al. (2006)
NR 2600 MgO H3PO4 9 100 95 Iaconi et al. (2010)
Municipal 200 1150 MgO Triple 9.5 87 98 Suschka and
wastewater superphosphate, Poplawski (2003)
H3PO4
24 1400 MgCl2 H3PO4 8.5 NR 97 Türker and Celen
(2007)
273 193/168 MgCl2 – 9.14 87 46 Demirer and
Othman (2009)
50–170 100–700 MgCl2 – 8.5 95% NR Pastor et al. (2010)
21 949 MgCl2 H3PO4 9 95 89 Uysal et al. (2010)
54 795 MgCl2 KH2PO4 8.5–9 NR NR Latifian et al. (2012)

Sewage 15–27% NR MgCl2 NH4Cl 10 97 NR Xu et al. (2012)
sludge ash
831
an alternative to deal with issues related to their excess nutrient load. The average
total P content in dairy, poultry, and pig manures are 9.3, 18, and 39 g kg1,
respectively (Barnett 1994; Shen and Shen 2011). Among farm-based wastes,
successful struvite recovery has been reported in dairy manures, swine manure,
poultry manure, and cattle urine.
Though P load of manures makes these suitable sources, P fractionation between
available and non-available is an issue. Manure contains P mostly as inorganic P
(60–90%). The rest of the P contained in manure is in the organic P fraction, and it
remains the most poorly studied potential source for P recovery (Barnett 1994).
Further, particulate P that remains mostly bound to mineral component is unavailable
for recovery (Sharpley and Moyer 2000; Chapuis-Lardy et al. 2003). Hence, the use
of some pretreatment methods (acid/base leaching, chelating agent treatment, micro-
wave treatment, anaerobic digestion) in order to release P into an available form is
helpful for making struvite recovery more effective in manures (Shen et al. 2001;
Szogi et al. 2008; Moody et al. 2009; Qureshi et al. 2008). However, in farm-based
waste, though availability and abundance of P are ensured, economics of incorpora-
tion of pretreatment methods has to be considered for effective struvite recovery.
Industrial wastes: Most of the input nutrient load in industrial processes makes
their way into the effluent coming out. However, the environmental regulations in most
countries are becoming stringent in the use of appropriate technology to reduce the P
content of waste streams before safe disposal. In this context, recovery of P from high-
strength industrial effluents is a viable strategy for their safe disposal by stripping both P
and NH4+ concentration (Altinbas et al. 2002). Successful struvite recovery has been
reported from wastewater from tanning, food processing, slaughterhouse and meat
packing, tannery, textile, dye, cola beverage, fertilizers and agrochemical, semicon-
ductor, rare earth, yeast, and coking industries (Table 2). However, orthophosphate
concentrations of these sources remain in the lower side compared to manures, which
makes external supplementation of P sources a must in most of the cases to make the
crystallization effective. Similarly for sources with less NH4+ (e.g., such as cola
beverage, fertilizer industry wastewater), NH4+ is needed to add externally (Xu et al.
2012; Hutnik et al. 2012; Foletto et al. 2013). Literature reported direct use of industrial
wastewater for struvite recovery without pretreatment.
Municipal waste: It is the spontaneous precipitation of struvite in municipal
sewer system that led to controlled struvite recovery attempt using other wastes also.
Globally huge quantity of municipal water is produced annually which contains high
amounts of nutrients and organic materials (Guo et al. 2010). Phosphorus from both
domestic and industrial sources enters the municipal wastewater treatment plants.
Phosphate can be recovered from the liquid phase (supernatant liquor of anaerobic
digestion), sludge phase, and mono-incinerated sludge ash as shown in Fig. 6
(Cornel and Schaum 2009). Ninety percent of the incoming phosphorus load, from
the wastewater, is incorporated into the sewage sludge. The phosphorus recovery
rate from the liquid phase can reach up to 40–50%, while recovery rates from sewage
sludge and sewage sludge ash can reach up to 90% (Cornel and Schaum 2009). The
economically feasible recovery requires a liquid phase containing 50–60 mg l1of
ortho-P (Cornel and Schaum 2009).
Primary Secondary
sedimentation sedimentation
Activated sludge
Anaerobic
anoxic aerobic
pretreatment
1a
Anaerobic
posttreatment
2a 2b
Anaerobic
Dewatering Incineration 3
digestion
1b
1a: side stream after anaerobic treatment; 1b: dewatering unit after anaerobic digestion;
2a: sludge from the digestor before dewatering; 2b: sludge from the digester after dewatering;
3: sewage sludge ash after incineration
Fig. 6 Possible locations for phosphorus recovery in wastewater treatment plant (Adapted from
Desmidt et al. 2015)
Prior to struvite recover, fixation of P in wastewater sludge particles requires use

of some pretreatment methods (acidic, basic, microwave, enhanced biological phos-
phorus removal) (Stark 2005; Pan et al. 2006; Pastor et al. 2008). Landfill leachate
(Li and Zhao 2003; Kim et al. 2006; Iaconi et al. 2010) and human urine (Ganrot
et al. 2007; Morales et al. 2013, Hug and Udert 2013) are also prospective sources
for struvite recovery, which can be directly used without any pretreatment. Urine-
derived struvite is found to be free of heavy metal, and alkali addition is not required
due to its inherent alkaline nature (Hug and Udert 2013; Morales et al. 2013).
Combustion ash of municipal sewage sludge could be another prospective struvite
source, but recovery process needs incorporation of mechanical, thermal (incinera-
tion), or chemical pretreatments (Hong et al. 2005; Xu et al. 2012).
From Tables 1, 2, and 3, it is seen that, when the constituting elements are found
to be limiting, the requirements are fulfilled by external addition of P and NH4+ salts.
Most of these studies used stirred batch reactors which are frequently used to provide
necessary mixing energy at small scale due to operational simplicity and reasonable
recovery efficiency, whereas, at pilot scale, fluidized bed reactors are generally used.
The pH range found to be favorable for struvite precipitation varies from of 8 to
11, which is generally adjusted using NaOH, MgO, KOH, or CO2 stripping. Recov-
ery efficiency of P and ammonium as struvite is usually >90%.
To understand the measure of suitability of a waste for struvite recovery based on
its composition, a Feedstock Suitability Index (FSI) has been developed, which has
been reported in previous publication by the authors (Kataki et al. 2016a). The index
takes into account concentration of P, ammonia as favorable component, whereas
concentrations of inhibiting ions such as Ca and Fe are considered to affect FSI
Table 4 Ranking and Rank Feedstock

Feedstock Suitability
1 Rare-earth wastewater
Index (FSI) of potential
struvite recovery sources 2 Fertilizers industry wastewater
(Adapted from Kataki 3 Cochineal insects processing wastewater (carmine dye
et al. 2016a with industry)
modification) 4 Nylon wastewater
5 Human urine
5 Leather tanning wastewater
6 Cola beverage
7 Landfill leachate
8 Coking/coke oven wastewater
9 Poultry manure wastewater
10 AD effluent of molasses-based industrial wastewater
11 Dairy manure
12 Semiconductor wastewater
13 Pharmaceutical wastewater
14 Municipal wastewater
14 Swine wastewater
15 Yeast industry wastewater
16 Anaerobic effluent from potato processing industries
17 Textile printing industry wastewater
18 Abattoir wastewater/slaughterhouse wastewaters
negatively. If compositional status of a particular waste source is known, the FSI

index is expected to be useful in identifying comparative suitability of different
waste sources for struvite production. As per the FSI index, rare earth wastewater is
found to be the most suitable source; however, its abundance could be an issue.
Among the top potent sources of struvite showing high FSI, urine appears to be a
promising source considering its composition and reliable availability (Table 4).
Commercial Processes
Several studies have evaluated the potential technologies of P recovery at bench and
pilot scales, and only a few has been incorporated in full-scale system. A limited
number of commercial struvite recovery units handling urine and municipal waste-
water sludge are in operation in countries like Nepal, Japan, Canada, England, the
USA, Australia, Germany, the Netherlands, and Italy. In these commercial processes,
to make the recovered struvite competent with chemical fertilizer, the recovered
struvite is washed, dried, purified, concentrated, sieved/sorted for granulometry,
milled or pelletized, and packaged. Descriptions of some commercially available
struvite recovery technologies are given below, and Table 5 summarizes the over-
view of these processes.
Table 5 Overview of commercial processes available for struvite recovery
32
Available/
Year of initiation/ Reactor place of Mg source/pH P recovery
Process Input developed by type operation adjustment efficiency pH Pellet size Remarks
Airprex Digested sludge from EBPR Berliner CSTR The MgCl2, 80–90 8 – –
WWTP Wasserbetriebe Netherlands, CO2stripping
Germany
Phospaq Rejection water of wastewater 2007/Paques BV CSTR The MgO/ 80% 8.2–8.3 0.7 mm Struvite
treatment Netherlands, CO2stripping complies with
Germany EU standard
Combined
phosphate and
COD removal
Pearl Centrates from digested sludge 2007/University of Fluidized Canada, UK MgCl2/NaOH 85% 7.25 – –
from EBPR WWTP British Columbia/ bed
Ostara
Crystalactor Centrates from digested sludge DHV Water BV Fluidized The Sand, NaOH, 70–80 8–8.5 0.8 mm No residue
from EBPR WWTP bed Netherlands H2SO4, Ca Need of high
(OH)2 turbulence
Potato processing Compact
high-purity
crystal
Stuttgart Digested sludge 2003–2004 – Germany – – – – –
NuReSys Dairy industry, potato 2006/Akwadok CSTR Germany, MgCl2/NaOH 72–90 8–8.5 – Modular
processing industry, bvba Belgium, the assembly
pharmaceutical, municipal Netherlands
wastewater
Phosnix Wastewater after digestion or 1987/Unitika Ltd. Fluidized Japan MgOH/ 80–90 8.2–8.8 0.5–1 mm –
sludge treatment bed NaOH
Seaborne Digested sludge 2000/Seaborne CSTR Germany H2SO4, Na2S, 90 – – Separation of
Environmental NaOH, MgO, heavy metal

Research flocculent problematic
Laboratory
Multiform Food processing, farm (dairy, 2012/Multiform Fluidized USA MgCl2/NaOH 80 – – –
swine) waste Harvest Inc. bed
835
Anaerobic
effluent
MgCI2 NaOH
Air Effluent
STRIPPER
CRYSTALIZER
Crystal Purge
Fig. 7 Schematic overview of the NuReSys process (Adapted from Moerman et al. 2009)
NuReSys (Belgium): NuReSys (Nutrients Recovery Systems) is a Belgian-

based company founded in 2011. The technology has been applied in case
of digested sludge, dairy industry, and food processing industry. The main common
features of the reactors are air stripper, crystallization reactor equipped with a
top entry mixer and a transient quiescent settling zone, and pH control (using
NaOH) (Fig. 7) (Moerman et al. 2009). The struvite pellets are harvested by
intermittent purging, and up to 76% of P removal could be achieved (Moerman
et al. 2009).
Pearl ® Technology (North America, UK): The US patented Pearl ® Technology
for struvite (commercially known as Crystal Green) was developed by the University
of British Columbia, Canada. In Oregon (USA) the first commercial full-scale plant
was installed in 2009. Ostara process is primarily applied to recover phosphorus
from dewatering liquor and centrate after anaerobic digestion. Ostara technology
utilizes upflow fluidized bed reactor comprising a liquid/solid separation device, a
settling tank and a reaction tank, and a piping system and an injector arranged to
inject chemicals (Fig. 8). Phosphorus and ammonia recovery using this technology
was reported to achieve 80–90% and 14–42%, respectively (Britton et al. 2009;
Oleszkiewicz 2015).
Phospaq™ (The Netherlands): The technology was developed by Paques, the
Netherlands. The technology is commercially being used in Lomm (in potato pro-
cessing industry) and Olburgen (in potato processing industry and municipal waste-
water plant) of the Netherlands (Remy 2013). A PO43 recovery efficiency of 75%
and NH4+ recovery of 19% could be achieved using this technology (Remy et al.
2013). The struvite complies with EU standards for fertilizer. Recovery of struvite by
Treated
centrate
Magnesium effluent
Chloride
(MgCI2)
Caustic
Crystal
Centrate
GreenTM
Influent
Product
Fig. 8 Schematic overview of the Pearl technology (Adapted from Britton et al. 2009)
PHOSPAQ™ is feasible from a daily P load >100 kg P/d, ortho-P load >50 mg/l,
and NH4+ load >200 mg/l (Paques 2016). The advantage of the process is combined
phosphate, ammonia, and COD removal in one reactor.
Phosnix (Japan): The Phosnix process was developed by Unitika Ltd. (Katsuura
1998) and has been in operation in Japan since 1987 (Münch and Barr 2001). The
reactor consists of an aerated column containing a fluidized bed of granulated
struvite, into which returned water from sewage sludge treatment is fed (Fig. 9).
Recirculation of the effluent back to the initial wastewater treatment reduces the
requirement for chemical supplementation (Ueno and Fuji 2001; Nawa 2009).
Seaborne (Germany): The Seaborne process was developed by the Seaborne
Environmental Research Laboratory, Germany. This combined treatment technology
with multiple unit operations uses anaerobic digestion and sludge acidification by
sulfuric acid to extract nutrients and heavy metals from the solid phase, followed by
heavy metal precipitation as metal sulfide. After that, struvite is precipitated by
addition of magnesium hydroxide and NaOH (to increase the pH to pH 9) in a
continuous stirred tank reactor (Fig. 10). However, sometimes, ineffective removal
of heavy metals may result in struvite with impermissible heavy metal concentration
through this technology (Müller et al. 2007; Bergmans 2011).
AirPrex™ (Germany, Netherlands): The AirPrex™ technology was developed
by Berliner Wasserbetriebe and was implemented at the Wassmannsdorf wastewater
treatment plant (Heinzmann and Engel 2006; Forstner 2015). A continuous stirred
tank reactor is utilized in this technology where sludge is lifted upward by air
bubbles in the aerated zone. Struvite is continuously removed from the bottom of
pH
Treated Water
Separation Digestion Tank

Zone
Mg(OH)2 NaOH
Struvite Separator P Storage P Storage Digested Sludge
Tank Tank
Recovered
Struvite Granule Formation Zone
Dehydrator
Fines are returned to Raw Water
Struvite Granule Formation
Column
Hopper
Struvite
B
Blower P
Feed Pump Storage
Sold as Raw Material for Fertilizer Tank
Fig. 9 Schematic overview of the Phosnix process (Ueno and Fuji 2001)
Fuel Flue gas
acid Ash
incineration
Digested sludge
Drying
Ammonium- NaOH acid
sulfate
Polymer Centrifuge
org. Wasterwater
stripping
Residues to the inflow
of the wwtp
Filter
Gas desulphurised
to the block and Filter
Digester Gas heat power plant
Mg(OH) NaOH
2
Centrifuge
Filter
Residues
MgNH4PO4
(Heavy Metal-
Sulfides)
Fig. 10 Process flow sheet of the Seaborne process at the (Müller et al. 2007)
tank. Sand washing equipment is utilized to ensure cleaning and purification of the
recovered struvite (Desmidt et al. 2015; Oleszkiewicz 2015). These plants were
reported to remove 80–90% of phosphate from the liquid phase of the digested
sludge (Desmidt et al. 2015) (Fig. 11).
Digested Sewage Sludge
MgCI2
AirLife Reactor
Polymer
Decanter Dewatered Sludge
Air Sludge Liquor
Struvite sludge
Water Sand Process Water

Washer
Struvite
Fig. 11 Schematic overview of the AirPrex technology (Adapted from www.p-rex.eu)
Multiform (America): The patented Multiform technology was developed by

Multiform Harvest Inc. The technology is commercially operational at wastewater
treatment plants in Boise, Idaho, and the city of Yakima, Washington. The technol-
ogy is also suitable for food processing and swine farm waste. The technology is
reported to achieve an 80% and a 20% reduction in phosphate and nitrogen from
wastewater, respectively (www.multiformharvest.com). This reactor consists of a
conical shaped fluidized bed with no recycle flow (Fig. 12). Struvite pellets are
collected from bottom of the reactor (Oleszkiewicz 2015). Bowers and Westerman
(2005) demonstrated from laboratory-scale experiments that phosphorus removal
process was optimal at pH 7.56 with 60 mg l1 Mg using this technology.
Stuttgart: The technology was developed at the Institute of Sanitary Engineer-
ing, Water Quality and Solid Waste Management of the University of Stuttgart,
Germany. The process is distinguished by the fact that municipal sewage sludge
from wastewater treatment plants with simultaneous phosphate elimination with
iron salts could be used without any changes in the process of wastewater purifica-
tion. Though not much information about the field-level application is available
about this technology, more information is available at www.iswa.uni-stuttgart.de.
The pilot plant consists of two batch tanks, a sedimentation tank, and a chamber
filter press as well as holding tanks and dosing equipment for the operational
resources (Fig. 13).
Fig. 12 Schematic overview of the multiform technology
Crystalactor: This patented Crystalactor technology was developed by DHV, the

Netherlands. The Crystalactor is a cylindrical fluidized bed reactor where wastewater
is pumped in an upward direction, achieving up to 95% of P reduction (Fig. 14). The
reactor is partially filled with a suitable seed material like sand or minerals. High
crystallization rate is also reported to be achieved with concentrated solutions
(>100 mg P l1) (Oleszkiewicz 2015); however, the influent rate must be constant
during the treatment, as an increase can lead to an increase of secondary nucleation
or a decrease not sufficient to maintain particles in a fluidized state (Regy et al.
2002). Furthermore, some amorphous phosphate is lost in suspended form; there-
fore, a dual-media filtration is required, which incurs additional capital and opera-
tional costs.
Fig. 13 Schematic overview of the Stuttgart technology
Fig. 14 The Crystalactor process flow diagram
Effects of Nonparticipating Ions on Crystallization
Most waste sources comprise a heterogeneous mix of nutrients and ions, and certain
nonparticipating ions can limit the struvite precipitation process. In typical wastes P
can exist in particulate or suspended form and in soluble and insoluble form, often in
association with other components (Le Corre et al. 2005; Marti et al. 2008). There
are various impurities including aluminum ions, alkali metal ions (potassium,
sodium), alkali earths (calcium), transition metals (iron, copper, zinc), anions (sul-
fates, chlorides, nitrates, fluorides, carbonates), and organic impurities (lactic acid)
which impact on crystal growth kinetics (Table 2). These soluble cations provide
background competition to precipitate Mg or Ca phosphates and therefore have
potential to contaminate the product or decrease the product yield. Metal ions mostly
compete for phosphate ions and coprecipitation of their salts (mostly phosphate or
hydroxide) salts along with struvite can reduce product purity (de Bashan 2004).
Further, crystals growth is inhibited because of blockage of active growth sites
through adsorption of impurity ions onto the surface of struvite crystals (Jones
2002; Kabdasli et al. 2006).
Crystal size can be decreased by up to 46% in the presence of impurities
like calcium, iron, and nitrates (Hutnik et al. 2011). The ions can affect negatively
the growth rate and can lengthen the induction time preceding the first occurrence
of crystals (Koutsoukos et al. 2003; Kabdasli et al. 2006). Impurities in solution are
also known to affect the growth rates of crystalline compounds due to blocking of
sites where crystals could formed, thus inhibiting the increase of crystal size
(Jones 2002).
In waste sources like animal manures, where Ca levels are relatively high, Ca
ions can interact with phosphate or carbonate ions to form calcium phosphates
(usually as apatite, hydroxylapatite) or calcium carbonates (usually calcite)
(Le Corre et al. 2005). Interference from calcium can be minimized by either
thermodynamically driven redissolution of calcium phosphate or by removing it
via chemical precipitation at elevated pH (Huichzermeier and Tao 2012) (Tables 6,
7, and 8).
Technology Enhancement Through Process Modification
Though laboratory feasibility for struvite precipitation is shown from a range of

sources, full-scale installations are still limited. At present, municipal wastewater sludge
and human urine are the two sources where commercial struvite recovery is carried
out. Successful execution of recovery possesses some difficulty related to heterogeneous
characteristics of source, chemical input, and recovery efficiency, making the
overall struvite economics unfavorable. Therefore, in the recent literature, there is an
increasing concern toward the techno-economical aspects of the process to increase the
process efficiency and cost affectivity such as improved and competent method of
production, effect of different seed material, and alternative and recyclable magnesium
sources.
Methods of Struvite Recovery
With time some advanced techniques have come up using established principles of
electrochemistry, ion exchange separation, and biomineralization by microbes. The
new approaches are developed to make the process more efficient in terms of
recovery, which are discussed below.
Table 6 Effect of nonparticipating ions on struvite precipitation (Adapted and expanded from
Kataki et al. 2016b)
Ion Effect on struvite recovery Reference
Phosphocitrate Inhibition was dose dependent leading to complete Wierzbicki et al.
cessation at higher concentration (1997)
Phosphocitrate induces very strong, crystal face-
specific inhibition of struvite
Acetohydroxamic Crystal growth is slowed Downey et al.
acid Disrupt struvite growth and formation directly through (1992)
interference with the molecular growth processes on
crystal surfaces
Ca Formation of amorphous Ca phosphate when Mg/Ca Le Corre et al.
>1:1 (2005)
Decrease in struvite purity when Ca/Mg >1 Wang et al.
Precipitation of Ca phosphate at pH >10 (2013)
Significant reduction in struvite precipitation (by 37%) Pastor et al.
in municipal sludge containing 59 mg L1 Ca (2008)
compared to sludge with 10 mg L1 Ca
Decrease in crystal size with increase in Ca Hutnik et al.
concentration and formation of tubular crystal (2011)
Coexistence of hydroxylapatite in product
Insignificant change in P recovery efficiency Huichzermeier
Loss of product purity at Ca/P >0.5:1 and Tao (2012)
Increased fine (<1 μm) production with increase in Ca Lee et al. (2013)
concentration
Na Increase in induction time at concentration over Kabdasli et al.
50 103 mol dm3 (2006)
CO32 Marginal increase in induction time Kabdasli et al.
(2006)
Removes Ca as CaCO3 and increases struvite Huichzermeier
formation potential and Tao (2012)
SO42 Increase in induction time Kabdasli et al.
(2006)
Lactic acid Formation of untypical long and thin crystals Kozik et al.
No adverse impact on crystal development (2011)
Fe Coprecipitation of Fe hydroxides Hutnik et al.
With increase in Fe2+ concentration decrease in mean (2012)
crystal size (by >20%)
Decrease in homogeneity in product
Formation of tubular crystal
NO32 With increase in NO32 concentration and decrease in Hutnik et al.
mean crystal size (by 29%) (2013)
Cu Moderate increase in crystal size (by 6%) Hutnik et al.
The presence of Cu hydroxide in product (2013)
(continued)
Table 6 (continued)
Ion Effect on struvite recovery Reference
Zn Appearance of Zn impurity in product as hydroxides, Kozik et al.
phosphates, other salt (2013)
K Appearance of K impurity in product as hydroxides, Kozik et al.
phosphates, other salts (2013)
Al Appearance of Al impurity in product as hydroxides, Kozik et al.
phosphates, other salts (2013)
Humic substance Inhibition effect is pH dependent Zhou et al.
(fulvic acid) Inhibition is reduced with increase in Mg/P ratio (2015)
Coprecipitation of humic substance reducing purity
Change in crystal morphology
Herbal extracts Juice of Citrus medica Linn and the herbal extracts of Chauhan and
Commiphora wightii, Boerhaavia diffusa Linn, and Joshi (2013)
Rotula aquatica Lour were tested and found to be
potent inhibitors
Chemical Precipitation
Chemical precipitation is the most common method (>95% literature) of struvite

precipitation. In these types of processes, struvite is crystallized in the reactor by the
addition of chemicals, to reach the optimum molar ratio Mg/P. The pH required to set
off the nucleation is typically adjusted by alkaline addition, while a propeller is used to
mix the solutions and favor the occurrence of struvite crystals. A settling zone is
integrated to the reactor to allow for the accumulation of particles. To provide adequate
mixing energy, stirred batch reactors are most frequently used, particularly in small-
scale laboratory investigations as they are simple in operation and installation (Kabdasli
et al. 2000; Kim et al. 2006; Zhang et al. 2009; Xu et al. 2012; Foletto et al. 2013). At
larger scale, fluidized bed reactors are commonly used as the design gives provision for
sufficient reactive surface area and solution turbulence (Seckler et al. 1996). The main
advantage of chemical precipitation methods is their operational simplicity; however,
production of non-recoverable, fine struvite particles is a common problem in these
reactors (Adnan et al. 2003). Moreover, coprecipitation of other salts (such as calcium
phosphate) due to the presence of foreign ions is another issue (Capdevielle et al. 2013).
Other limitations include low solubility of chemicals like MgO and KOH, energy-
intensive step CO2 stripping method, loss of ammonia from aeration, and inputs
accounting for a large share of the total production cost (Cusick et al. 2014).
Electrochemical Methods
This method is based on the principle of electrochemical precipitation, where an

electrochemical cell is used with an anode made of platinum, graphite, or carbon-felt
disks and a cathode of nickel, a platinum-carbon, or a steel plate. Deposition of struvite
Table 7 Comparative overview of commercial struvite recovery processes (Modified from Kataki
et al. 2016b)
Chemical Electrochemical
Specifications precipitation deposition Ion exchange Biomineralization
Principle Precipitation of P Deposition of P and NH4+ are Precipitation
and NH4+ in struvite on a exchanged in ion through
solution with cathode in a exchangers and biomineralization
addition of Mg solution precipitated as in medium
and mixing containing Mg, struvite upon Mg containing PO43
PO43, and NH4+ addition and Mg, utilizing
through NH4+ from N
electrochemical metabolism by
reaction microbes
pH Chemical additive Self- Chemical additive Self-established
(NaOH, KOH) establishment of (NaOH) alkalinity
alkalinity
Mixing Stirring, fluidizing Stirring, fluidizing Not applicable Not applicable
Reactor Stirred batch, Electrochemical Ion exchange Batch culture
fluidized bed cell column
1.1.Limitation 1. Coprecipitation 1. Coprecipitation 1. Coprecipitation 1. Coprecipitation
of impurity as salt of impurity of impurities of impurity
2. Ineffective 2. Use of costly 2. Regeneration of 1.2. Slow
crystallization for material like Pt resin at regular precipitation
not meeting intervals
suitable conditions
3. Production of 3. Scale formation 3. Limited
fines on cathode availability of
specific anion
exchangers for
PO43 sorption
Advantage Easy to install and No need of alkali Fast precipitation No external
operate addition, addition of alkali
Does not employ concurrent
the use of production of
sophisticated potential H2 fuel
equipment
Installation At commercial/ At laboratory At laboratory scale At laboratory scale
laboratory scale scale
Demonstration In real (manure, In real (sludge, In synthetic waste In synthetic waste
sludge, ash) and digestate)/
synthetic wastes synthetic waste
Large share of Alkali source, Mg Cathode material, Ion exchange resin Mg source
cost source electrical energy
takes place on the cathode from an analyte solution containing Mg, PO43, and NH4+
ions. In this process chemicals are not required for pH adjustment as hydrogen gas is
concurrently released during the electrolytic reduction of water at the cathode during
the process (Moussa et al. 2006; Wang et al. 2010). In this process, hydrogen recovery
for other uses could offset the operational costs of the process (Cusick and Logan 2012).
846
Table 8 Overview of pretreatments used in struvite recovery

Principle Materials used Factors affecting Used in Limitation
Acid/base Acidification causes protonation of Acid/base (HCl, H2SO4) Type and Dairy, Higher metal
leaching phosphate ions from bound phosphates composition of poultry contamination
(Ca/Mg/Fe phosphate), lowers their ionic material
product below their equilibrium solubility Type of acid/base,
product which results in dissolution of pH, temperature
particulate P into solution
Chelating The ligands react with the calcium Ethylenediaminetetraacetic Type of source Dairy Process needs
agent [Ca-PO4] particulates to form soluble acid (EDTA) manure optimization, as excess
treatment [Ca-EDTA or Ca-oxalate] complexes and Oxalic acid chelate might subsequently
eventually PO43 is released (Zhang et al. bind to Mg limiting Mg
(2010)) availability
Concerns regarding
environmental toxicity and
expense
Enhanced Enhanced biological phosphorus removal P-accumulating microbial Waste characteristics Sewage Vulnerability of
biological P process is based on the ability of strains sludge accumulated P to get
removal P-accumulating microorganisms to uptake released from microbial
P into their cells from a surrounding mass during sludge
medium handling.
Temperature, Less efficient for wastes
microbial population with higher Ca contents
Microwave Microwave digestion of sources under Microwave, oxidants, Forms of P present, Dairy Temperature and time
treatment specific temperature and duration acids, and bases microwave manure should be effective
solubilizing particulate P operating
temperature, and
duration of heating
In recent works, microbial electrochemical cells have been used to help in phosphate
mobilization during struvite recovery (Fischer et al. 2011). Where waste source has a
high inorganic phosphate (FePO4, Al(PO4)3) content, such as in digested sewage
sludge, microbial fuel cells mobilize phosphate by reducing the inorganic phosphate
using energy from microbes, liberating the phosphate into solution (Fischer et al.
2011). Retention of unwanted heavy metals that are retained in sludge matrix in
immobilized form is an advantage of the process (Fischer et al. 2011). Further, where
a high dose of Mg is required, Mg can itself be used as anode (Hug and Udert 2013;
Kruk et al. 2014) making the process cost effective (Hug and Udert 2013). The use of
precious metals like platinum and cathode deterioration by struvite accumulation are
the limitations of the process (Hirooka and Ichihashi 2013; Cusick et al. 2014).
Ion Exchange Methods
This method is based on the principle that nutrients from wastewaters are selectively
exchanged in ion exchangers and struvite is precipitated after addition of Mg2+ at
controlled pH (Liberti et al. 1986, 2001; Mijangos et al. 2004, 2013; Ortueta et al.
2015). The important factors influencing the process are the eluent concentration and
selection of ion exchange resin (functional group of resin and matrix of ion
exchanger) (Mijangos et al. 2013; Ortueta et al. 2015). Commercial-level application
of this method is not very extensive. Availability of specific anion exchangers for
phosphate sorption is the main limitation of this process (Petruzzeli et al. 2004).
Moreover, the high suspended solid content of regenerated effluent may cause
fouling of the exchange columns (Gonder et al. 2006).
Microbial Biomineralization Methods
Certain bacterial strains (e.g., Myxococcus xanthus, Staphylococcus aureus) can

precipitate struvite in a medium containing PO43 and Mg through the process of
biomineralization. NH4+ required for precipitation is produced from microbial
metabolism of the nitrogenous compounds present in the medium or precipitating
solution (Omar et al. 1998; Gonzalez-Munoz et al. 1996; Omar et al. 1998). Apart
from living microbial cells, dead cells, disrupted cells, and isolated bacterial struc-
tures (cell membrane) can also induce struvite crystallization by acting as substrates
for heterogeneous nucleation for crystallization (Gonzalez-Munoz et al. 1996; Omar
et al. 1998). Organic matrix of disrupted bacterial cells has been reported to be rich in
negatively charged multimolecular complexes (proteolipids, phospholipids, glyco-
protein, proteoglycan) and attracts positive ions like Mg resulting in struvite precip-
itation (Gonzalez-Munoz et al. 1996; Omar et al. 1998). The effectiveness of
microbial production of struvite depends upon the microbial growth phase (Lopez
et al. 2007). Parameters related to culture medium (pH, total phosphorus, and total
nitrogen) used for microbial growth have direct impact on the amount of struvite
produced (Da Silva et al. 2000) (Fig. 15).
a Nutrient rich b
waste source
Base
Mg2+ Mg2+
Stirrer
PO43– NH4+ STRUVITE

NH4+
PO43– pH
PO43– N mineralization
PO43–
NH4+
Organic N Organic N Organic N
PO43– 3–
PO43– PO 3– PO4 4
B B B
Struvite PO43– B PO43–
B B B
Bacteria
Struvite
c NaCI
d Nutrient rich
waste source e
CI– Na+ e
2+
Mg
e
CI– CI– Na+ Na+
CI– CI– Na+ Na+ H2O+e

–
1/2 H2+OH–
Resin
CATHODE
ANODE
bed pH
CI– CI– Na+ Na+
Anion Cation pH
exchanger exchanger O2+2H2O+4e
–
4OH
–
PO43– 2– HPO42–
HPO4
PO43–
3–
HPO4
2–
3–
PO4
PO4
PO43–
Mg2+ NaOH PO43– NH4+
NH + Struvite
NH4+ 3–4
PO 4 PO43–
Regenerate
Elute
Struvite
Fig. 15 Schematic diagrams showing (a) chemical, (b) microbial, (c) electrochemical, and (d) ion
exchange method used for struvite precipitation (Adapted from Kataki et al. 2016b)
Use of Different Pretreatments for Maximizing Struvite Recovery
In many conventional and prospective sources (farm wastes, municipal wastes and
wastewater, and industrial wastes), P remaining in available or recoverable form is
often at a minimum because of its fixation with other ions. This makes the recovery and
crystallization process challenging. Therefore, such sources may require additional
pretreatment to improve the initial phosphate solubility to achieve maximum P recov-
ery, which are discussed below.
pH Modification Using Acid/Base Leaching
Acidification (using hydrochloric acid, sulfuric acid) dissolves P into solution

enhancing P availability for struvite formation (Zhang et al. 2010). Pretreatment
by acidification has been used in dairy manure (P availability increased by 500%)
(Zhang et al. 2010), dairy manure (43–100% of total P released) (Shen et al. 2001),
poultry manure (increase of 60–80% of total P) (Szogi et al. 2008), and sewage
sludge (release of 80–100% of total P) (Stark 2005). The degree of P leaching is
affected by the type and composition of material under treatment, the acid/base
added, pH, and temperature (Stark 2005). It has been reported that higher amount of
base is required compared to acid to leach same amount of P (Mrowiec et al. 2003).
However, acid leaching gives higher metal contamination in waste effluents as acids
can leach out other metal ions along with P (Stark 2005).
Chelating Agent Treatment
Use of chelating agents like ethylenediaminetetraacetic acid (EDTA) and oxalic acid
has been reported as a pretreatment method prior to struvite formation. Chelating
agents help to release particulate PO43 by sequestering calcium from it and thereby
suppressing the formation of calcium phosphate compounds (Shen et al. 2001).
Zhang et al. (2012) reported increase in dissolved P of up to 93% by EDTA treatment
in digested dairy manure, and Zhang et al. (2015) achieved removal of 97% of
soluble Ca by calcium oxalate precipitation after using oxalic acid in dairy manure.
Such treatments are suitable for waste sources with rich Ca such as farm manure;
however, the quantity of chelates needs to be optimized as it might limit Mg
availability by binding to it (Zhang et al. 2010; Shen et al. 2001). Further, concerns
about environmental toxicity remain with some chelates.
Microwave Heating
A number of studies reported the use of microwave irradiation pretreatment method

for enhanced struvite recovery (Liao et al. 2005; Pan et al. 2006; Chan et al. 2007;
Qureshi et al. 2008; Kenge et al. 2009; Lo and Liao 2011; Xiao et al. 2015). The
factors affecting the degree of P release are forms of P present, microwave operating
temperature, and duration of heating (Liao et al. 2005; Pan et al. 2006). An optimum
temperature of 120 C has been suggested as optimum by Chan et al. (2007) in
sewage sludge. Uniform heating throughout the material with precise control over
process temperature, achievement of high heating rates, and no direct contact
between heating source and material under treatment are some of the advantages
of microwave treatment over conventional heating (Lo and Liao 2011). It has been
reported that the efficiency of the treatment method can be enhanced by addition of
chemical-assisted (oxidants, acids, and bases) microwave digestion (Pan et al. 2006;
Chan et al. 2007; Qiao et al. 2008; Qureshi et al. 2008).
Enhanced Biological Phosphorus Removal (EBPR)
Enhanced biological phosphorus removal process can accumulate 80–90% of P

present in surrounding medium into microbial biomass. This results in up to 12%
of P concentration in EBPR sludges, whereas for conventional sludge, it remains
2–3% (Liao et al. 2005). The use of EBPR sludge as struvite source has been
demonstrated in previous literature (Britton et al. 2005; Pastor et al. 2008; Shen
et al. 2001) reporting 58–94% of P recovery (Munch and Barr 2001; Britton et al.
2005; Marti et al. 2008). However, the recovery efficiency varies depending upon
sludge characteristics, temperature, and microbial population (Pastor et al. 2008).
Use of Seed in Struvite Crystallization
Seed acts as template by providing surface area and thus reduces induction period for
crystal development. Among the reported seed materials in struvite recovery, struvite
is the most widely investigated (Table 9). Effect of seeding on struvite was reported
to have no significant effect to significant effect. Earlier investigations by Regy et al.
(2002) and Rahaman et al. (2008) found no significant effect of seed on struvite
crystallization. The studies concluded that the newly formed crystal nuclei provide
greater surface area for new crystal development than the seed crystals resulting in
no effect under seeded condition (Regy et al. 2002). However, the use of struvite
seed was found to enhance recovery by 5% and crystallization rate up to 21%
compared to unseeded crystallization in studies by Zhang et al. (2009) and Yu
et al. (2013). An isomorphic crystal plane of struvite seed promotes adhesion and
integration of growing molecules and clusters of struvite without the need of
nucleation, which makes the process energetically favorable resulting in enhanced
P recovery efficiency. Further, isomorphic crystal of seed struvite intensifies crys-
tallization minimizing induction time (Liu et al. 2011a). In struvite recovery from
fertilizer wastewater, induction time is reduced by 75 min using struvite seed
compared to unseeded condition (Liu et al. 2011a). Though, in recent literature,
some alternative seeds such as sand, stainless steel, pumice stone, borosilicate glass,
etc. are used, studies reported lower crystallization rates and higher induction time
under non-struvite seed (Ali 2005). The reason could be changes in the type of
nucleation from homogeneous to heterogeneous under non-struvite seed (Ohlinger
et al. 1999; Ali 2005).
The factors affecting seed’s effectiveness are its surface roughness, size, dosing of
the seed, and supersaturation of crystallizing (Ohlinger et al. 1999). Increasing in
dose and grain size of struvite seed usually has a positive effect on struvite formation
(Huang et al. 2010a). In saponification wastewater, ammonium removal efficiency is
increased through formation of struvite from 84% to 91% when struvite seed size is
increased from 0.05–0.098 to 0.098–0.150 mm. The efficiency is further enhanced to
92% when the dose is increased to 60 g/l (Huang et al. 2010a). Liu et al. (2011a)
showed that, at a seed dosing of 0.422 g l1, the induction time is less by 49 min in a
solution with higher supersaturation compared to a solution with lower
Table 9 Different seed material used in struvite precipitation and their effects on recovery
(Modified and expanded from Kataki et al. 2016b)
Seed Size
Seed used (μm) Effects on struvite production Reference
Struvite 1000 Production of struvite fine as product Regy et al.
Seeding is insignificant (process appeared “self- (2002)
seeding”)
45–63 Crystals have similar shape with seed (no phase Ali (2005)
transformation during growth)
75–150 Effectiveness of seed requires consideration of Kim et al.
pH (pH 9 being optimum) (2006 )
NR Enhancement of crystallization by 19% at low P Liu et al.
concentration (2008a)
Increased crystal size, settle ability
250–500 No enhancement of P recovery and reduction in Rahaman
induction time et al. (2008)
NR Increase in recovery by approximately 5% Zhang et al.
(at pH 9.5) (2009)
No effect of overdosing of seed on recovery
(pH 9.5)
NR Reduction in induction time up to 75 min Liu et al.
depending upon supersaturation (2011a)
30–50 Similar shape of struvite with seed Mehta et al.
(2013)
NR Increase in rate of crystallization (by 21%) and Yu et al.
size of crystal (from 1.72 nm to 2.08 nm) (2013)
Coarse sand 200–300 No fixation of struvite on sand surface Regy et al.
(2002)
Fine sand 150–200 Strong primary nucleation and formation of fine Regy et al.
(2002)
Borosilicate 45–63 Slower reaction rate compared to struvite seed Ali (2005)
glass
Sand grain/ 210–350 Recovery of 80% of P onto seed bed Battistoni
quartz et al. (2000)
particle 45–63 Slower reaction rate compared to struvite seed Ali (2005)
Phosphate NR No effect mentioned on crystal Massey et al.
rock (2007)
Stainless 1000 um No significant increase in crystallization Le Corre
steel mesh hole Reduction in struvite fine particle et al. (2007)
Pumice stone NR No effect of seed dosing on recovery Pakdil and
Coprecipitation of Ca and silica on seed Filibeli
(2008)
supersaturation. However, struvite crystallization with seeding material is an energy-

and cost-intensive process as amounts of seed requirement are often high to make
crystallization effective. Although tested in synthetic liquor, feasibility of the use of
most of the novel seeds is yet to be tested with real waste.
Alternative Magnesium Sources for Struvite Precipitation
Struvite recovery needs input of chemical and indispensible consumption

of Mg source make the precipitation often expensive (Chimenos et al. 2003;
Lee et al. 2003). In majority of recovery sources, addition of Mg is routinely required
due to their low inherent content. The most used Mg sources are salts of Mg, such
as MgCl2, MgSO4, MgO, and MgOH. It has been reported that high cost of -
high-grade Mg compounds has limited its full-scale implementation, contributing
up to 75% of overall production costs (Dockhorn 2009). Some studies investigate
the effectiveness of some alternative and recyclable Mg sources to
minimize the process cost (Table 10). Mainly the aspects of Mg availability, reagent
solubility, and reactivity of the Mg source play a significant role on the feasibility of
its use.
Bittern and seawater are two novel Mg sources reported in struvite recovery.
Struvite recovery efficiency in coke manufacturing wastewater using seawater
and bittern is reported to be 95% and 99% of total P, respectively (Shin and Lee
1997), which is comparable with recovery by conventional Mg salts. However,
because of the presence of insoluble Mg in bittern or seawater, process needs high
Mg dose (>1.5:1) for efficient P recovery (Matsumiya et al. 2000; Kumashiro
et al. 2001; Quintana et al. 2004). However, Ca ion prevalent in seawater
could interfere in recovery process. Seawater and bittern have been shown
effective for struvite precipitation in swine wastewater, coke wastewater, urine,
landfill leachate, and municipal wastewater. Magnesite (MgCO3), a by-product of
MgO production (Chimenos et al. 2003; Quintana et al. 2004), is another pro-
spective Mg source. However, magnesite has low solubility in water, requiring
high dose for struvite precipitation. Acid dissolution and thermally decomposed
magnesite can be more effective as Mg source (Gunay et al. 2008; Huang et al.
2010b).
Thermal decomposition or pyrolysis product of struvite, viz., MgHPO4 and
Mg2P2O7, can also be used as recycled Mg source (Zhang et al. 2009; Huang et al.
2009; Yu et al. 2012). Process is further modified by using struvite pyrolysis under
alkali condition (Türker and Çelen 2007; He et al. 2007; Zhang et al. 2009; Yu et al.
2012), which produces MgNaPO4 as per reaction 1 (Huang et al. 2011b). It is
estimated that the use of struvite pyrolysate can save up to 44–48% of process cost
(He et al. 2007; Huang et al. 2009). Struvite recovery by struvite pyrolysate in
landfill leachate (maximum 96% NH4+ removal) was achieved under optimum
conditions of OH/NH4+ of 1:1, temperature of 90 C, and time of 2 h as reported
by He et al. (2007); however, the conditions vary with recovery source. It has been
reported that, in the subsequent recycling cycles of struvite pyrolysate, the NH4+
removal ratio decreases (He et al. 2007; Huang et al. 2011b) because of accumula-
tion of inactive Mg2P2O7 and Mg3(PO4)2 (Sugiyamaa et al. 2005; Yu et al. 2012),
which can be improved by acidolysis of pyrolysate (Zhang et al. 2004; Yu et al.
2012).
Table 10 Alternative Mg sources used in struvite recovery (Adapted and expanded from Kataki
et al. 2016b)
Mg source Mg content Key findings Reference
Bittern 31,390 mg l1 Similar recovery efficiency as MgCl2 Shin and Lee
(1997)
9220–24,900 mg l1 Comparable struvite precipitation Li and Zhao
efficiency with MgCl2 and MgSO4 (2002)
32,000 mg l1 Bittern is more effective in P recovery Lee et al.
than NH4+ recovery (2003)
27,500 More cost effective in coastal areas Etter et al.
(2011)
Seawater 1136 mg l1 Same P recovery efficiency as MgCl2 Shin and Lee
(1997)
1250 mg l1 Higher Mg/PO43 (>1.5:1) necessary Matsumiya
for more than 70% P recovery et al. (2000)
1250 mg l1 Higher Mg/PO43 (>1.5:1) necessary Kumashiro
for stabilized and easy P recovery et al. (2001)
1200 mg l1 Similar recovery efficiency as MgCl2 Lee et al.
(75%) (2003)
Thermally 676.7 g kg1 Need higher Mg/PO43 molar ratio for Quintana
decomposed effective recovery et al. (2004)
magnesite
Brucite 650 g kg1 Brucite can be used as liquid and solid Huang et al.
Mg source; reuse of brucite is possible (2011a)
Magnesite 300 g kg1 Acid dissolution of magnesite increase Gunay et al.
struvite recovery by 50% (2008)
940 g kg1 Thermal decomposed magnesite is cost Huang et al.
effective than acid-dissolved magnesite (2010)
244 g kg1 Cheaper than bittern and MgSO4 Etter et al.
(2011)
Struvite pyrolysate 530 g kg1 Similar effects on recovery as with Huang et al.
Mg salt (2011b)
Wood ash 34 g kg1 Presence of impurity such as calcite, Sakthivel
heavy metal in product et al. (2011)
Synthetic 146 mmol l1 Effective as Mg source but pH and Zewuhn
nanofiltration of organic matter influence purity of et al. (2012)
brine from product
seawater
Desalinated reject 1555–2795 mg 1 Presence of other ions (Ca, Na) in Fattah and
water reject water reduces recovery Ahmed
efficiency (2013)
Mg(II) solution 8000 mg 1 Higher dose of Mg/PO43 (>1:1) has Lahav et al.
from seawater no effect on recovery (2013)
Calcined dolomite 36% 89.7% of NH4+ recovery Chen et al.
(MgO/CaCO3 The competition between K and (2017)
suspension) NH4+also led to formation of
K-struvite (MgKPO4.6H2O)
decreasing NH4+ removal rate
Application of Struvite as Soil Fertilizer
Fertilizer Properties of Struvite
As fertilizer, the N, P, K, and Mg content of struvite are 5.7:29:0:16.4, respectively

(Westerman 2009). The P content of struvite remains in the range of 11–26%
(Johnston and Richards 2003) depending upon source and method of production,
of which 1–2% is water soluble and rest is citrate soluble (Bridger et al. 1962). It is
used by fertilizer companies as additive or as a substitute raw material in standard
fertilizer production technology (Li and Zhao 2002; Rafie et al. 2013). The cost of
such commercial product largely depends upon processing (drying, storage, creation
of a blended product) and transportation (Westerman 2009).
The most desirable properties of struvite as fertilizer is its slow nutrient release
characteristics. Struvite is sparingly soluble in water with a solubility of 0.02 g
100 ml1 of water at 0 C, rendering its slow assimilation into soil solution (Li and
Zhao 2002; Negrea et al. 2010). The N leaching rate of struvite is threefold lower
compared to commercial N fertilizer (Rahman et al. 2011). Slow nutrient release
from struvite allows its high rate of application without damaging plant roots (Li and
Zhao 2002; Rafie et al. 2013). Due to its prolonged release of nutrients throughout
the growing season, often a single application is sufficient to meet crop nutrient
demand. However, literature indicated two concerns in this context: (i) sometimes
the limited availability of N because of low N/P2O5 ratio of struvite makes N
insufficient for optimal plant growth (Miso 2009; Gell et al. 2011), and (ii) when
the application dose is increased to fulfill N requirement, it is shown to increase soil
pH compared to other P fertilizers, which might affect nutrient availability and
uptake (Rahman et al. 2011).
The fertilizing effect of struvite varies with soil type due to differences in
solubility and sorption properties of the soils. Struvite is most effective in soil of
moderate or low pH, but its effectiveness is limited in soils with marginal fertility
and high pH. Struvite solubility is minimum (0.040 mM) at pH 8.2–8.8 (Le Corre
et al. 2009), which can rise up to 1–10 mM at pH below 5 (Borgerding 1972;
Abbona et al. 1982). Because of similar solubility of struvite with triple superphos-
phate, struvite was found to have similar effect as in acid and neutral soil (Cabeza
et al. 2011). However, in alkaline calcareous soil also, struvite is found to be more
soluble, making it a recommended P fertilizer (Massey et al. 2007). It has been
reported that, compared to chemical fertilizer-treated soil, leaching of N from
struvite-treated soil is lower, but there is no significant variation in P leaching
(Rahaman et al. 2011).
Quality standard of struvite can be described in terms of its crushing strength,
composition, and purity which is influenced by source, processing (drying), and Mg
addition (Antonini et al. 2012). Multicomponent raw material of struvite like sewage
sludge usually contains a number of heavy metals (Cd, Cu, Cr, Ni, Pb, and Zn)
and organic micro-pollutants. However, there is a lack of information on residual
impurity in recovered struvite from various sources (Wollmann and Moller 2015).
Previous literature reports impurity content of struvite from municipal wastewater to

comply with fertilizer regulatory limit in different countries like Germany and Turkey
(Uysal et al. 2010; Antonini et al. 2012; Forrest et al. 2008; Latifian et al. 2012).
Crushing strength is a quality parameter for struvite as fertilizer which predicts its
handling and storage properties. The average size of commercial struvite crystals
generated is 2–3.3 mm in size depending upon reactor conditions, viz., upflow
velocity, pH, and supersaturation ratio (Forrest et al. 2008).
Effect of Struvite Application on Crop
Recently a reasonable number of studies have come up to establish the fertilizer

value of struvite on a range of crops, considering its properties, composition, effect
on soil and plant, and comparative performance with chemical fertilizer. These
studies reported the use of struvite on diverse crops including vegetables, ornamen-
tal, forest outplanting, turf, orchards, and potted plants.
It is evident from previous studies that there is no significant difference between
P in struvite and water-soluble P in other phosphate fertilizers, as most of the
studies reported comparable effect of struvite as fertilizer with chemical fertilizer
(Ghosh et al. 1996; Johnston and Richards. 2003; Li and Zhao. 2003; Plaza et al.
2007; Massey et al. 2009; Perez et al. 2009; Liu et al. 2011b; Gell et al. 2011;
Dalecha et al. 2012). Urine-derived struvite was found to produce yield and
phosphate uptake comparable to those induced by phosphate fertilizer when tested
with ryegrass, Zea mays L., and red clover (Simons 2008; Antonini et al. 2012).
Instead, in some literatures, struvite has been reported to yield better results in
comparison with some conventional fertilizers such as ammonium phosphate,
diammonium phosphate, and single superphosphate (Barak and Stafford 2006;
Gonzalez-Ponce et al. 2009; Yetilmezsoy et al. 2013). When compared with single
superphosphate, urine derived struvite is found to be more effective in lettuce yield
with enhanced P uptake, which was probably related to its higher Mg content and
the synergistic effect of Mg on P uptake (Gonzalez-Ponce et al. 2009). It has also
been reported that P concentration is higher in plants treated with struvite than in
plants treated with other P fertilizers (Li and Zhao 2003; Gonzalez-Ponce and
Garcia-Lopez 2007). While comparing the effect of struvite with phosphate rock,
monoammonium phosphate, and calcium superphosphate on potted ryegrass,
P accumulation is found to be highest in struvite-treated perennial ryegrass
(Gonzalez-Ponce and Garcia-Lopez 2007). Three-year field experiments with
MAP showed no statistically significant benefit in terms of increased grain yield
over unfertilized soil or phosphate rock (Weinfurtner et al. 2009), and pot exper-
iments suggest struvite has a relative fertilizer efficiency of 64–134% of TSP
(Perez et al. 2009). However, there are some studies which reported lower yield
in struvite-treated plants because of lower availability of nutrients compared to
chemical fertilizer (Ganrot et al. 2007; Ackerman et al. 2013). Therefore, supple-
mentation of chemical fertilizer along with struvite has been recommended for
Table 11 Effect of application of struvite as fertilizer on various crops (Adapted and modified
from Kataki et al. 2016b)
Crop/plant Struvite source Remark Reference
Gram (Cicer Synthetic water Variation of P uptake with level of Ghosh et al.
arietinum L.) P application (1996)
Superior or equally effective as
chemical fertilizer
Chinese flowering Municipal Similar vegetable growth and Li and Zhao
cabbage (Brassica landfill leachate more Mg and P uptake compared (2003)
parachinensis) to chemical fertilizer
Water Municipal No significant difference in growth Li and Zhao
convolvulus landfill leachate and no burning effect with (2003)
(Ipomea increase in struvite dose
aquatica, Higher dose of struvite does not
I. reptans) affect plant
Water spinach Municipal Similar vegetable growth and Li and Zhao
(Ipomoea landfill leachate more Mg and P uptake compared (2003)
aquatica) to chemical fertilizer
Chinese chard Municipal Similar vegetable growth and Li and Zhao
(Brassica rapa landfill leachate more Mg and P uptake compared (2003)
var. chinensis) to chemical fertilizer
Maize NR P uptake efficiency for struvite is Barak and
117%, and residual P availability Stafford (2006)
is 178%
Higher efficiency compared to
chemical fertilizer
Swine Similar plant height, higher Liu et al.
wastewater biomass, and less N2O emission as (2011b)
with chemical fertilizer
Urine No significant difference in dry Gell et al. (2011)
yield compared to chemical
fertilizer
Black water No significant difference in dry Gell et al. (2011)
yield compared chemical fertilizer
Urine Similar leaf diameter and height Dalecha et al.
with chemical fertilizer (2012)
Corn fiber Plant P uptake is higher than Thompson
processing chemical fertilizer by 4–21% (2013)
wastewater depending upon application rate
Nutrient availability is similar to
chemical fertilizer
Wheat (Triticum Urine Lower dry weight (by 50%) than Ganrot et al.
aestivum L.) chemical fertilizer (2007)
Dairy Low availability of nutrients Massey et al.
wastewater (N) than chemical fertilizer (2009)
Increase in total P uptake in basic
soil
(continued)
Table 11 (continued)
Perennial Municipal Similar increase in dry matter and Plaza et al.
ryegrass (Lolium sewage sludge P uptake compared to chemical (2007)
perenne) fertilizer
Synthetic liquor Similar dry matter yield and P Johnston and
and municipal uptake as with chemical fertilizer Richards (2003)
sewage sludge
Poultry manure Increase in fresh and dry weight by Yetilmezsoy and
76% compared to 60% in control, Zengin (2009)
faster growth than with control
Increase in weight and rate of
increase is dependent upon type of
plant and soil media
White lupin Wastewater Equal P uptake and higher Mg Gonzalez-Ponce
(Lupinus albus uptake compared to P fertilizer and Garcıa-
L.) Lopez-de-Sa
(2008)
Oilseed rape Municipal Higher P uptake and grain yield Perez et al.
sewage sludge compared to synthetic fertilizer/ (2009)
rock phosphate
Purslane Poultry manure Increase in fresh and dry weight by Yetilmezsoy and
(Portulaca 150% compared to 207% in Zengin (2009)
oleracea) control, faster growth than with
control dependent upon type of
plant, soil media
Garden cress Poultry manure Increase in fresh and dry weight by Yetilmezsoy and
(Lepidium 28% compared to 115% in control, Zengin (2009)
sativum) faster growth than with control
Winter barley Municipal Similar P uptake and grain yield Perez et al.
sewage sludge compared to chemical fertilizer/ (2009)
rock phosphate
Lettuce (Lactuca Anaerobically More efficient than chemical Gonzalez-Ponce
sativa L.) digested fertilizer in increasing yield and P et al. 2009
municipal uptake
sludge liquor
Garden rocket Anaerobic More gain in plant wet, dry Yetilmezsoy
(Eruca sativa) sludge of weight, and height compared to et al. (2013)
poultry manure chemical fertilizer
Dill (Anethum Anaerobic Increase in dry weight by 191% Yetilmezsoy
graveolens) sludge of compared to no fertilizer et al. (2013)
poultry manure
Fennel Anaerobic Increase in dry weight by 208% Yetilmezsoy
(Foeniculum sludge of compared to no fertilizer et al. (2013)
vulgare) poultry manure
Parsley Anaerobic Increase in dry weight by 379% Yetilmezsoy
(Petroselinum sludge of compared to no fertilizer et al. (2013)
crispum) poultry manure
Canola Swine manure Similar P uptake but lower Ackerman et al.
biomass yield/unit of P uptake (2013)
(continued)
Table 11 (continued)
compared to chemical fertilizer
because of lower solubility at basic
soil
Supplement with chemical
fertilizer might need depending
upon soil type
Tomato Yeast industry Higher N, P, and Mg uptake of Uysal et al.
wastewater plant for double/triple and (2014)
quadruple dose of struvite
compared to NPK treatment
Higher (more than double) dose of
struvite is essential for optimum
effect
better results (Ackerman et al. 2013). Further, chemical P fertilizer-treated crop is

shown to have better yield compared to struvite, which has been attributed to a
potential potassium deficiency as reflected in crops (Hammond and White 2005).
Its application enhances P uptake, as the Mg present in it has a synergistic effect on
P absorption (Gonzalez-Ponce et al. 2009).
From the above discussion, it is seen in previous research reports that there is
variation in the fertilizing effect of struvite with no significant impact on plants
but with significant effect on P and Mg uptake and biomass yield. The findings
are subjected to various factors such as soil type, plant type, and climate behav-
ior, keeping further scopes on its application at larger scale corresponding to
these factors. However, considering the associated benefits of struvite recovery
process, struvite recovery appears to be an attractive and feasible alternative
(Table 11).
Conclusions
Here we have analyzed and reviewed outcomes of different studies addressing

suitability and prospects of waste streams of various origins for struvite production,
methods of recovery, commercial struvite recovery, strategies for enhanced and
effective recovery (pretreatments, alternative Mg source, seed), and their application
prospects for comprehensive understanding of evolution in this field.
Struvite recovery, as a method of nutrient recycling, has expansive multifaceted
benefits and is receiving support from R&D. Potential of struvite recovery from farm
wastes, municipal and industrial wastes remain highly attractive with a high P
recovery efficiencies (~85 to 95%). In recent years, development of techno-
economically efficient method from alternative potential struvite sources with incor-
poration of more efficient method, Mg source, and seed material remains the
mainstream research focus. However, while a range of laboratory-scale struvite
recovery experiments were found to be successful, development of cost-effective,

targeted, and environmentally friendly full-scale installations is still a challenge due
to inherently heterogeneous nature of the sources and unfavorable economics, which
requires further research and development. On the other hand, study on its applica-
tion aspect identifies its favorable impact, though more intense research on field trial
is required with region-specific focus for long-term effects and with a wide range of
test crops. Further, strategy for struvite market development should focus on a
holistic approach considering pricing, purity, quantities, size, storage, transportation,
distribution, and infrastructure, in view of the legal framework of contaminants,
eco-toxicity, and hygiene, so that value-added products can be developed to recycle
P into the nutrient cycle and can be used as a supplement to prevailing nutrient
supply system. The developmental impacts of such technological successes would
be profound for global food security in terms of alternative and sustainable fertilizers
for crop.
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Global Status of Nitrate Contamination
in Groundwater: Its Occurrence, Health 33
Saurabh Shukla and Abhishek Saxena
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 870
Occurrence of Nitrate in Various Ecosystems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 871
Anthropogenic Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 873
Geogenic Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 875
Status of Nitrate Contamination in Groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 876
Global Status . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 876
Status in India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 878
Health Impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 879
Methemoglobinemia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 880
Cancer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 881
Thyroid Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 881
Impacts on Livestock Health and Aquatic Life . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 881
Removal Technologies of Nitrate from Drinking Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 882
Removal Through Carbon-Based Adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 882
Removal Through Natural Adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 883
Removal Through Sorbents Obtained from Agricultural Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . 883
Removal Through Sorbents Obtained from Industrial Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 883
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 884
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 885
Abstract
Nitrate has emerged as one of the most alarming and widespread contaminant of
groundwater and surface water resources reported around the globe. Nitrate
formation is an integral part of nitrogen cycle and is added either by the natural
processes (atmospheric fixation, lightning storms) or through anthropogenic
activities (fertilizer applications, septic tanks). Nitrate enters the hydrosphere
S. Shukla (*) · A. Saxena

e-mail: saurabh.shukla2020@gmail.com

https://doi.org/10.1007/978-3-319-73645-7_20
870 S. Shukla and A. Saxena
easily, and its ingestion causes various health risks such as methemoglobinemia,
cancer, diabetes, etc. on humans and to some extent on livestock populations as
well. Agricultural practices and subsequent fertilizer application along with other
anthropogenic activities are assumed to be the primary reason behind elevated
levels of nitrate in groundwater. However, even under the similar ecological
conditions, the reported occurrence of nitrate in groundwater is sporadic in nature,
indicating the possible interference from other complex factors (including
geogenic factors) and a dynamic release mechanism. Various concepts for the
different sources and occurrence of nitrate in groundwater along with its health
impacts are discussed in this chapter. Several existing and upcoming technologies
are there to remove excess nitrate from potable water; these are also discussed in
the chapter.
Keywords
Nitrate contamination · Sporadic occurrence · Geogenic sources ·
Methemoglobinemia · Groundwater pollution · Indo-Gangetic alluvium ·
Anthropogenic sources · BATs · Removal technologies · Adsorption · Activated
carbon · Industrial waste · Agricultural waste
Introduction
Groundwater, which serves as the only drinking source in many parts of the world
(Zekster and Everett 2004), is one of the most precious natural resources. It is also
the world’s most extracted raw material with withdrawal rates in the range of
982 km3/year (Margat and Gun 2013). The total volume of fresh groundwater stored
on earth is believed to be in the region of 8–10 million km3, which is more than 2000
times the current annual withdrawal of surface water and groundwater combined
(Gun 2012). Generally, fluctuating water levels in shallow groundwater, within a
relatively short time scale, can be used as an indicator of land use stresses that may
affect deep aquifer systems as well, with passage of time. The groundwater quality
deterioration can be attributed broadly to two mechanisms, (i) anthropogenic and
(ii) geogenic (Lapworth et al. 2017), and during the last two decades, nitrate (NO3)
contamination in groundwater has become highly discussed worldwide, and it is the
second most common threat after pesticides (Spalding and Exner 1993). Nitrate,
nitrite (NO2), ammonia (NH3), and organically bound forms of nitrogen (Org-N)
are the species of concern for water resource management (Anayah and Almasri
2009; CGWB 2014) around the globe. The background nitrate concentration in
groundwater shall not exceed 10 mg/L as nitrate or 2 mg/L as nitrate-nitrogen,
NO3-N (Mueller and Helsel 1996). The levels exceeding this background limit
are an indicator of nitrate contamination, primarily through various anthropogenic
activities (Wongsanit et al. 2015). Although this background concentration cannot be
considered of pristine state, the contribution from geogenic sources of nitrate cannot
be ignored in comprehensive analysis.
33 Global Status of Nitrate Contamination in Groundwater: Its Occurrence. . . 871
Table 1 Permissible limit of nitrate in drinking water by different agencies

Concentration as Concentration as
Country/organization NO3 - N (mg/L) NO3 (mg/L) Source
WHO 11 50 WHO
(2011)
United States Environmental 10 45 EPA
Protection Agency (2012)
BIS – 45 IS: 10500
(2012)
The guideline value for nitrate in drinking water, prescribed by various agencies,
is summarized in Table 1 to protect against methemoglobinemia in bottle-fed infants
(WHO 2011). The WHO guideline value of 50 mg/L is based on epidemiological
evidence for methemoglobinemia in infants, which results from short-term exposure
and is protective for bottle-fed infants and, consequently, other population groups
(WHO 2011).
Various studies have been conducted around the world, and the presence of
geogenic factors along with anthropogenic ones makes nitrate contamination of
groundwater an intricate challenge. The aim of this chapter is to present a review
on the nature of occurrence of nitrate in groundwater, global status, its dynamic
release mechanism, various health impacts, and the existing and upcoming removal
technologies.
Occurrence of Nitrate in Various Ecosystems
Formation of nitrates is an indispensable part of the environmental nitrogen cycle.

Globally, approximately 260 million tons of atmospheric nitrogen is being fixed.
Biological fixation accounts for 67.25% of nitrogen fixed per year (through land
(legume and nonlegume) and sea (Table 2). The remaining 32.75% is fixed through
non-biological processes such as atmospheric lightning and industrial discharges
(Miyamoto et al. 2008). This nitrogen fixed in the soil undergoes the process of
ammonification (Fig. 1) and gets converted to ammonium, which is further
converted first to nitrite (undergoing the process of nitrification) and then to nitrate
(through the action of nitrifying bacteria).
Nitrate are also formed when aerobic and anaerobic bacteria along with other
microorganisms present in soil break down decaying dead plants and animals,
fertilizers, and other organic residues and convert these to ammonium ion, which
is subsequently converted to nitrate (Fig. 1). This converted nitrate undergoes
assimilation and is utilized by plants to satisfy nutrient requirements and may
accumulate nitrate in their leaves and stems. Sometimes rain or irrigation water
can leach them into groundwater as nitrate-containing compounds are generally
soluble and readily migrate into groundwater (Self and Waskom 2014).
Table 2 Estimated Source of N fixation Nitrogen fixed (106 tons per year)
amounts of nitrogen
Land 153
fixed annually from
different sources Legume 39
(Source: Miyamoto Nonlegume 10
et al. 2008) Others 104
Sea 40
Total biological 193
Lightning 9
Industry 85
Total non-biological 94
Sedimentary
N2
Organic Matter
Denitrification
tion
Fixa
Mineralization
Organic N N2O
Assimilation
NH4+ NO2− NO3−

Nitrification
NH4+ mineral NO3− mineral
Fig. 1 Geologic nitrogen cycle (Adapted from Holloway and Dahlgren 2002)
Some of the major factors controlling nitrate concentrations in saturated zone

groundwater can be characterized using land-use type, chalk formation, borehole
depth, effective precipitation, and groundwater level (Roy et al. 2007).
Various ecosystems have the nitrogen accumulation and transfer potential
(Fig. 2). The accumulation potential is the ability to retain the nitrogen within the
respective ecosystem, and transfer potential is the ability of the respective ecosystem
to allow the migration of nitrogen into another ecosystem. The nitrogen accumula-
tion and transfer potential varies from one ecosystem to another and can be used as
an invariably good indicator of risk of nitrite and nitrate contamination in these
ecosystems. The increasing nitrate concentration has adverse effects on various
ecosystems and may cause algal bloom and subsequent eutrophication, increase in
NOx emissions (Galloway et al. 2003; Zhou et al. 2011), etc. The comparison of this
accumulation and transfer potential for various ecosystems is presented in Fig. 2. It
may be seen here that, although atmosphere and agro-systems have low accu-
mulation potential, the high transfer potential presents a risk of contamination
Grasslands
Forests
Groundwater
Marine regions
Agrosystems
Wetlands, water bodies
Atmosphere
0 20 40 60 80 100
Low Low-Moderate Moderate High
Transfer Potential Accumulation Potential
Fig. 2 Nitrogen accumulation and transfer potential of different ecosystems (After Galloway et al.
2003)
in other ecosystems especially transferring into the groundwater. Similarly, high

accumulation and high transfer potential (grasslands and forests) present the risk of
nitrate contamination in groundwater through anthropogenic interventions.
Similar to other pollutants, nitrate also reaches the groundwater through anthro-
pogenic or geogenic sources. Although it is perceived that the contribution toward
elevated levels of nitrate in groundwater is primarily caused through anthropogenic
sources, which is true up to some extent, still the contribution from geogenic sources
also plays an important role in the nitrate contamination of groundwater resources.
Anthropogenic Sources
A larger fraction of groundwater nitrates is derived from various anthropogenic

sources, which are discussed below.
Fertilizer Application
Nitrogen is one of the major components of all the fertilizers, and with the advent
of various inorganic fertilizers, usage has increased to escalate the crop yield.
Overapplication and improper timing of applying the fertilizers cause the nitrates
to leach into the groundwater (Vinod et al. 2015). Fertilizer application and subse-
quent leaching is reported to have the highest contribution toward nitrate leaching
into the groundwater (Fig. 3).
Fig. 3 Anthropogenic
sources of nitrate 13%
contamination in groundwater
20%
7%
60%
Cropland Deforestation Industrial Waste
Domestic Wastewater & Septic Tanks
Human and Animal Waste

In areas of large human and animal populations, wastes generated by them are the
major source of nitrate pollution. The majority of urban population is provided with
sewerage systems; still many developing countries are using septic tanks/leaching
pits as decentralized sewage treatment. These in situ treatment systems have cus-
tomary leakage problems and contribute toward nitrate leaching into the ground-
water (Vijay et al. 2011). Open defecation and other such unhygienic sanitation
practices are also responsible for nitrate contamination in groundwater (Tambekar
and Neware 2012).
Generally, our concern toward the animal waste is limited to problems of odor,
flies, and impacts to surface water and surrounding areas; however, waste from
dairies, open feedlots, and other such facilities are a potential source of nitrogen and
other inputs to groundwater (CGWB 2014). Fecal waste from cattle population and
livestock farming also contributes toward nitrate pollution in groundwater (Sahoo
et al. 2016).
Industrial Uses of Nitrates

Several industries such as dye manufacturing units and metal processing industries use
various nitrogen-containing compounds such as (i) anhydrous ammonia, (ii) nitric acid,
(iii) urea, etc. The nitrogen in these compounds is converted to nitrite and nitrate.
Improper disposal of waste material generated from these industries have high proba-
bility of adding the nitrate concentration in the groundwater (Akwensioge 2012).
Explosives
Manufacturing of explosives involves use of ammonium nitrate and diesel as fuel.
Also, nitrogen is one of the chief constituent of explosives. The adversely affected
disposal streams having high concentration of ammonium nitrate and other
converted forms of nitrogen also add to high nitrate level in groundwater (Resende
et al. 2014).
Deforestation
The natural tendency of forest is to conserve and accumulate nitrogen in the soil pool
(Fig. 2); however, the transfer potential of forests is also high. The nitrogen is easily
converted to nitrate, and various anthropogenic interventions such as deforestation lead to
leaching of nitrate. This nitrate easily migrates into the groundwater because of high
nitrogen transfer potential of forests. Feichtinger et al. (2002) found that surface runoff
from forests have nitrate in the range of 0.1–20 mg/L. However, in certain Sierra forests
(USA), Miller et al. (2005) reported that the runoff immediately after rain had
150–400 mg/L of nitrate for very brief period of time. The high nitrate concentration in
these runoff water has high chance of contributing elevated nitrate levels in groundwater.
Among the anthropogenic sources, leaching from croplands and other agricultural
practices constitute the major contribution toward high nitrate concentration in ground-
water, followed by leaching from septic tanks and contribution from domestic waste-
water (Azizullah et al. 2011). The contribution from other factors such as leaching from
industrial waste and deforestation is marginally lower (Dahan et al. 2014). The approx-
imate percentage contribution of all these anthropogenic factors is illustrated in Fig. 3.
Geogenic Sources
The global mean nitrogen use efficiency by plants is approximately 50%; the
remaining nitrogen is lost into the environment (Rao and Puttanna 2006). The extent
of denitrification controls the leaching of nitrate into the groundwater through
natural processes (Stüeken et al. 2016).
Lightning Storms
Atmospheric nitrogen is first converted to ammonia and subsequently to nitrate and
is deposited to the soil generally through rainfall and other modes of precipitation,
during lightning storms (Galloway et al. 2004).
Geological Origin
Although often neglected in the past, geologic sources have been reported in recent
studies to comprise a large pool of nitrogen. There are several minerals like tobelite,
niter, and nitratine, etc., which have nitrogen in their lattice; this nitrogen is converted
to nitrate when it is released from the lattice during the process of weathering
(Holloway and Dahlgren 2002). The nitrate formed during weathering process may
leach down the aquifer strata and contaminate the groundwater (Holloway and Smith
2005). The geological nitrogen cycle is depicted in Fig. 1. In addition, nitrate from
mineral undergoes either assimilation (by biota) or reduction to nitrogen gases (N2 or
N2O) through denitrification (Holloway and Dahlgren 2002).
A study by Gupta et al. (2015) found high nitrate concentrations in the “river bank
filtration well” as well as in the groundwater samples in several zones of Srinagar
and Srikot area, where water in the adversely affected sites was exposed to zones of
bedrock. The isotopic composition of nitrate in water samples and leachates obtained
from these rocks (containing phyllites and quartzites) was found similar, confirming
that weathering and subsequent leaching of nitrate from these bedrocks have been
Fig. 4 Sources of nitrate in

groundwater
Nitrate Pollution
Anthropogenic
Dynamics of
Geogenic
the reason for elevated concentrations nitrate in water samples. Moreover, Power
et al. (1974) found that approximately 200 kg/ha of ammonium existed in a 1 m
thickness of the Paleocene Fort Union Shale in North Dakota and eastern Montana,
USA, which was found to be rapidly nitrified to nitrate under favorable moisture,
temperature, and oxygen concentration.
Other Geogenic Factors

There are several other factors, which contributes to the soil nitrates and subsequent
leaching into the groundwater; however, these might be very small in terms of concen-
tration. Precipitation brings down the nitrates and ammonium forms present in the
atmosphere, which are generally formed during combustion activities, volatilization of
fertilizers or animal wastes, etc. (Akwensioge 2012). In addition, factors like nature and
thickness of surface deposits, rainfall quantity and distribution, depth to the groundwater
level, distribution of vegetation types, and presence of nitrogen-fixing vegetation
(Lorenzen et al. 2012) also contribute toward the nitrate contamination in groundwater.
It is very well established through the reported studies that contribution of
geogenic sources of nitrate in groundwater is smaller when compared to anthropo-
genic sources (Fig. 4). Although anthropogenic activities alone cannot be exclu-
sively attributed toward the high nitrate concentration in soil, challenging analytical
methods and varying forms (organic/inorganic) make it difficult for quantification of
nitrate in rocks and groundwater (Holloway and Dahlgren 2002). This might be one
of the reasons behind the fewer number of studies investigating the geogenic origins
behind elevated levels of nitrate in groundwater.
Status of Nitrate Contamination in Groundwater
Global Status
Nitrate concentration above permissible limits in drinking water sources is a

common global phenomenon (Gong et al. 2013; Jiang et al. 2013). The association
between nitrate-contaminated well water and blue baby syndrome was first
described by Hunter Comly, who treated two infants for symptoms of

cyanosis during the early 1940s, in Iowa City, USA (Comly 1945). Both infants
became ill as they were fed with formulas that were diluted with water from shallow
wells. Nitrate concentrations in the related wells were 90 and 150 mg/L. Globally,
mean nitrate levels have risen by an estimated 36% in global waterways since
1990 with the highest increase seen in the Eastern Mediterranean and
Africa, where nitrate contamination has more than doubled. Several developed
and developing countries have been reported with elevated levels of nitrate in
groundwater. The developed countries have lower population density and hence
different land use patterns to those of developing countries; still similar trends of
nitrate contamination in groundwater resources have been reported around the
world.
Thorburn et al. (2003)) reported that 3% of the sampled wells were having nitrate
above 50 mg/L in northeastern Australia. A total of 5101 wells were sampled from
1991 to 2003 in 51 study areas throughout the USA, and more than 4% of the
sampled wells were having nitrate levels higher than EPA limit of 10 mg/L as nitrate-
nitrogen (Burrow et al. 2010). Shomar et al. (2008) found that more than 90% of the
groundwater wells sampled between 2001 and 2007 showed nitrate concentrations
up to eight times higher than the WHO permissible limit in Gaza strip. Similarly,
most of the local and regional aquifers in Europe are about to reach the guideline
value (50 mg/L) of nitrate as reported by Otero et al. (2009). A study in Afghanistan
(Houben et al. 2009) revealed that approximately 42% of the shallow groundwater
samples collected in Kabul had nitrate concentration more than 50 mg/L. Tagma
et al. (2009) found that more than 36% of the sampled wells in Chtouka-Massa
basin, South Morocco, exceed the value of 50 mg/L, and suggested the need of
further research for identification of the source. Cerdeira et al. (2008) reported higher
nitrate concentration (above MCL of 6 mg/L, given by São Paulo State law in Brazil)
in several urban downtown areas of Brazil. Fianko et al. (2009) reported that
more than 50% of the borehole samples had elevated levels of nitrate as nitrogen
(NO3-N). A total of 148 groundwater samples were collected from three different
zones in Osona, Spain (declared “vulnerable to nitrate pollution” by Catalon gov-
ernment), where nitrate concentration was found to be in the range of 10–529 mg/L
with a median value of 127 mg/L (Otero et al. 2009). Moore and Matalon (2011)
found that San Joaquin Valley is the epicenter of the nitrate contamination and more
than 75% of the samples collected from surface and groundwater sources located in
the valley were having nitrate concentration above WHO permissible limit,
impacting over 275,000 people. Several groundwater samples collected from
Gimpo agricultural area in South Korea had the average nitrate concentration of
79.4 mg/L, exceeding the Korean guideline value of 44.3 mg/L of nitrate (Cheong
et al. 2012). In some parts of Serbia, it is reported by Devic et al. (2014) that
groundwater pollution is caused by varying levels of nitrate, causing the water
quality falling to category III/IV which represents contaminated water, unsuitable
for human ingestion. Four alluvial floodplains in Europe have been reported with
high levels of nitrate by Antiguedad et al. (2016). Janjevic (2017) reported that water
from more than 28% of the 700 wells sampled in Germany had nitrate “exceeding
the legal limit of 50 mg/L.” Nitrate concentrations more than the 10 mg/L as
NO3-N are most common in eastern alluvial fans subregion in the Central Valley
of California, USA (Beutel et al. 2017).
Status in India
India is one of the topmost country when it comes to groundwater abstraction with an
estimated withdrawal rate of 251 km3/year reported in 2010 (Gun 2012). As per the
studies conducted by Rai (2003), approximately 117.93 million people in India are
drinking water with nitrates level 45–100 mg/L and 108.2 million people with levels
more than 100 mg/L of nitrate. A study revealed that more than 367 Indian districts
are affected by nitrate contamination above the BIS permissible limit in shallow
aquifers as shown in Fig. 5 (CGWB 2012). Jacks and Sharma (1983) found nitrate
concentrations as high as 1500 mg/L in Southern India, where higher concentrations
were more common in village wells than in the field irrigation wells. In Kanpur
district, more than 42% of the groundwater samples collected from shallow aquifers
and 26% collected from deep aquifers had been reported by Singh et al. (2006) to have
nitrate concentration exceeding the BIS limit. In Rajasthan, Suthar et al. (2009) found
out that the average nitrate was 60.6 33.6 (SD) mg/L in some agro-economy-based
rural habitation of northern parts of the state. Also, Shyam and Kalwania (2011)
found that nearly two-thirds of total samples had more than 50 mg/L of nitrates in
Sikar, Rajasthan. Dar et al. (2009) stated that 85% of samples during summers and
67% during winters were observed to have nitrates exceeding the permissible limit in
Sopore town, Kashmir, and attributed it toward the nitrogenous fertilizers use in the
area. Rai (2003) estimated that around 10.71 million people are drinking water with
nitrates level 45–100 mg/L and 3.47 million people with levels more than 100 mg/L
in Uttar Pradesh alone. Reddy et al. (2009) revealed that 65% of the samples were
found to be unfit for drinking purposes in the pre-monsoon season and 45% in post-
monsoon due to excess nitrate in north eastern part of Anantapur District, Andhra
Pradesh, where intense agricultural practices, improper sanitation, and organic waste
disposal methods were observed to contribute nitrate to the shallow and moderately
deep aquifers. A report by Central Ground Water Board (CGWB) reported that
groundwater in 42 district in Uttar Pradesh have more than 45 mg/L of nitrates with
mean value of 152 mg/L ranging between 47 and 1162 mg/L (CGWB 2012). Lokesh
(2013) found that more than 43% samples had higher nitrates than prescribed value in
Delhi and attributed it to fast urban growth and subsequent interventions.
Nitrate levels in groundwater over vast agricultural areas can be correlated with
intensive irrigated agriculture, corresponding use of nitrogenous fertilizers and
groundwater development, and consequent diffuse agricultural pollution has already
endangered the safety of potable groundwater for future generations in both rural
and urban areas. Most of the countries reportedly affected with nitrate contamination
in groundwater have almost 100% cropland and affected by heavy fertilizer appli-
cation; this is evident in Fig. 6, where areas with heavy fertilizer consumption and
having 100% cropland are marked with dark red color.
Fig. 5 Locations with nitrate >45 mg/L in shallow aquifers across India (Source: CGWB 2014)
Health Impacts
Nitrate assimilation in humans takes place via drinking water and having food, and it
becomes toxic when it is reduced to nitrite in the oral cavity (Lundberg et al. 2009).
Nitrate may enter the human body through endogenous and exogenous pathways,
N Fertilizer use Cropland

Heavy 100%
W E Miles Moderate 50%
0 2,000 4,000 8,000 Light 0%
S
Fig. 6 Global comparison of fertilizer application and availability of agricultural areas (Source
Potter et al. (2010, 2011))
where endogenous nitrate results from the circulation of nitrite and other nitrogen
oxides and exogenous nitrate enters via ingestion through food, drinking water,
inhalation, etc. (Fathmawati et al. 2017). Customarily, human ingestion of nitrate is
mostly from vegetables consumption, but more than 50% of nitrate intake may come
from drinking water sources when levels are above the maximum contaminant level
(DeRoos et al. 2003). Several studies have been conducted around the world
attempting to correlate the nitrate consumption and its various health impacts.
Ingestion of nitrate-contaminated water (NO3 >45 mg/L) may cause one or more
of the mentioned health impacts. This additive health impact depends upon the
exposure duration and ingested concentration of nitrate, and as the concentration
increases, the health risk also increases. These health impacts are discussed in the
following sections.
Methemoglobinemia
The most threatening of all the health impacts is “methemoglobinemia” also

known as “blue baby syndrome” which is caused when water with high nitrate
concentration is ingested in infants specially in “bottle-fed neonates” (WHO 2011).
When ferrous iron, in the blood, loses an electron and oxidizes to ferric iron,
hemoglobin is converted to methemoglobin (MetHb). MetHb reduces the oxygen
carrying capacity of the blood. There are various effects (Fig. 7) of formation of
methemoglobin in the human body because of ingestion of elevated levels of
nitrate, viz., cyanosis (decoloration of blood) and clubbing (appearance of blue
color in nails, tongues, etc.). A study by Sadeq et al. (2008) also reported that older
children (aged 1–7 years) drinking water containing more than 50 mg/L of nitrate
Fig. 7 Effects of methemoglobin production in human body, (a) central cyanosis, (b) clubbing, and
(c) change in blood color (Source: RamanaMurty 2013)
were significantly more likely to be affected by blue baby syndrome than those
drinking less than 50 mg/L of nitrate in drinking water.
Cancer
Nitrate is a precursor in the formation of nitrosamines. The International Agency for

Research on Cancer (IARC) classified nitrate as a probable human carcinogen (class
2A) that may form N-nitroso compounds (NOCs) through endogenous nitrosation.
Likeliness of strong carcinogenic effect of N-nitroso compounds (NOC) in humans
based on animal evidence of carcinogenicity in every species tested is also there
(Ashok and Hait 2015).
Thyroid Problems
Nitrate is a goitrogenic substance, and study by Eskiocak et al. (2005) suggested that
histomorphological changes in the thyroid are observed at 250 and 500 mg/L of
nitrate dosage. Many experimental studies suggest that nitrates impair thyroid
function involving the hypothalamo–hypophysio–thyroid axis.
Impacts on Livestock Health and Aquatic Life
Several studies suggested that, at levels between 100 and 200 mg/L, nitrate–nitrogen
in water causes decrease in appetite in livestock and asks for better management
practices to prevent livestock loss (Sahoo et al. 2016).
It has been reported that nitrate concentrations lower than the drinking water standard
cause substantial egg and fry mortality in some salmonid fish species (Kincheloe et al.
1979), whereas Alonso and Camargo (2013) found that nitrate did not cause mortality,
but it reduced the velocity of movement (at 44.9, 81.8 and 156.1 mg NO3-N/L) and
number of live newborns (in all tested concentrations) of aquatic snails.
Fig. 8 Different adsorbents for nitrate removal (Source: Bhatnagar and Sillanpaa 2011)
Removal Technologies of Nitrate from Drinking Water
Globally the most commonly accepted treatment technologies for nitrate removal
from drinking water includes chemical denitrification using zero valent iron and
magnesium (Ahn et al. 2008), ion exchange (IE) (Samatya et al. 2006), reverse
osmosis (RO) (Schoeman and Steyn 2003), electrodialysis (ED), and biological
denitrification (Soares 2000). WHO has suggested the use of ion exchange
(IX) process which requires waste brine disposal, and posttreatment is also required
to avoid corrosion of effluent and biological denitrification as nitrate removal
methods. While US EPA has suggested IE, RO (requiring high TDS disposal and
has a high operational cost and large volume of reject water), electrodialysis, as Best
Available Technologies (BATs) to treat nitrate-contaminated water (Bhatnagar and
Sillanpaa 2011). Various adsorbents used for nitrate removal are summarized in
Fig. 8 and are discussed in the following sections.
Removal Through Carbon-Based Adsorbents
Activated carbon (AC) is considered to be a universal adsorbent, and it removes

diverse types of aquatic pollutants. Powdered activated carbon (PAC) and carbon
nanotubes (CNTs) were also used for the removal of NO3, where removal capacity
of CNTs was found to be higher than PAC (Khani and Mirzaei 2008). Granular
activated carbon (GAC) obtained from coconut shells have also been examined for
NO3 removal, using steam activation process (Bhatnagar et al. 2008). The adsorp-
tion efficiency of bamboo powder charcoal (BPC) in nitrate removal from water has
been investigated by Mizuta et al. (2004), and he found that uptake values of BPC
and commercial activated carbon (CAC) at 10 C were 1.25 and 1.09 mg/g,
respectively, showing that the adsorption effectiveness of BPC was higher than
that of CAC regardless of the concentration of nitrate and test temperature.
Removal Through Natural Adsorbents
Clay being a natural sorbent can also be used for NO3 removal. Calcium bentonite
(CB) and calcium montmorillonite (CM) have been used, where CM, activated by
hydrochloric acid, showed better removal capacity (Mena-Duran et al. 2007). Xi
et al. (2010) found that poor and untreated clays such as Queensland bentonite,
kaolinite, and halloysite have shown poor adsorption capacity for nitrate removal.
These clay minerals when modified with hexadecyltrimethylammonium bromide
showed improved adsorption capacities.
The chitosan-coated zeolite (Ch-Z), protonated with either sulfuric or hydrochlo-
ric acid, has been tested for its ability to remove nitrate from potable water, where it
was found that protonation with hydrochloric acid resulted in a higher nitrate
removal capacity as compared to sulfuric acid (Arora et al. 2010).
Removal Through Sorbents Obtained from Agricultural Waste
Use of agricultural waste material is another option for nitrate removal and various
materials like wheat straw, raw wheat residue, sugarcane bagasse, and rice hull being
used for effective NO3 removal. Orlando et al. (2002) investigated the feasibility of
lignocellulosic agricultural waste materials (LCM), sugarcane bagasse (BG), and rice
hull (RH) for NO3 removal from water. The maximum removal capacity was obtained
from PL (1.8 mmol/g and 412.5%), followed by BG (1.41 mmol/g and 300%), PC
(1.34 mmol/g and 166%), and RH (1.32 mmol/g and 180%). A study compared the
removal capacity of raw wheat straw (RWR) and modified wheat straw (MWR) and
found that MWR had greater nitrate adsorbing capacity than RWR (Wang et al. 2007).
Removal Through Sorbents Obtained from Industrial Waste
A limited number of industrial wastes have been considered and tested for their
suitability to be used as nitrate removal adsorbents. Cengeloglu et al. (2006)
compared the nitrate adsorption efficiency of original and activated red mud (pro-
duced in alumina industries) and reported that removal capacity of activated mud
was higher than original mud. Several other industrial wastes such as slag, fly ash,
etc. have also been examined with other adsorbents and found to be useful in
removal of nitrate from water.
Selection of a suitable technology for nitrate removal from water generally
depends on several factors including (a) initial nitrate concentrations, (b) presence
Fig. 9 Comparison of some nitrate removal technologies (Source: Bhatnagar and Sillanpaa 2011)
and concentration of other ions, (c) adsorbent dose, and (d) variation of pH in water.
Thus, the selection of the appropriate technology/sorbent media can become a
tedious task. A comparative summary of some of these nitrate removal technologies
are shown in Fig. 9 (Shams 2010; Bhatnagar and Sillanpaa 2011).
Conclusion
Nitrate is one of the major contaminant of drinking water in most of the areas around
the world. Interestingly, the occurrence of elevated nitrate concentration in ground-
water is sporadic in nature, and even though having various advanced technologies
around the world, this problem is not addressed precisely in terms of its source as
well as the release mechanism. It is also clearly not evident that whether the nitrate is
leaching from fertilizers or minerals and the reason behind its release mechanism are
dynamic and complex. It is very well established that the low-cost filters and BATs
can be effectively used for the treatment of nitrate-contaminated waters. But the
problem doesn’t end with mitigation as it is an end of the pipe solution, and these
technologies create a stream of concentrated nitrates and also disposal problems.
There is a dire need of the hour to assess the extent of nitrate contamination in
groundwater on case-to-case basis and suitable control and remedial measures shall
be adopted.
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Remediation of Industrial and Automobile
Exhausts for Environmental Management 34
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
The Aim and Objective of this Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 891
Sources of Classification of Industrial and Automobile Exhausts and Disposal . . . . . . . . . . . . . . 891
Toxicity of Exhausts and their Release to Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 892
Possibilities of Remediation and Deactivation of Exhausts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 892
Significant Scientific Endeavor in the Field of Air Pollution Control of Industrial and
Automobile Exhausts and Industrial Wastewater Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 893
Visionary Scientific Endeavor in the Field of Environmental Management . . . . . . . . . . . . . . . . . . . 898
Environmental and Energy Sustainability and the Vast Vision for the Future . . . . . . . . . . . . . . . . . 902
Future Research Trends and Future Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 903
Conclusion and Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 903
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 904
Abstract
The world of environmental engineering science and environmental protection is
witnessing immense challenges today. Environmental management today stands
in the midst of immense scientific vision and vast introspection. Air pollution
control and industrial wastewater treatment in the similar manner are today in the
path of new scientific regeneration. In this paper, the authors deeply address the
vast scientific success of remediation of industrial and automobile exhausts for
environmental management. Human civilization’s immense scientific prowess,
S. Palit (*)
Department of Chemical Engineering, University of Petroleum and Energy Studies, Energy Acres,
Dehradun, Uttarakhand, India
e-mail: sukanchan68@gmail.com
C. M. Hussain
NJ, USA

https://doi.org/10.1007/978-3-319-73645-7_21
890 S. Palit and C. M. Hussain
the vast futuristic vision, and the technological vision of environmental engineer-
ing tools will all lead a long and effective way in the true emancipation of
environmental management today. Environmental and energy sustainability are
the other sides of the visionary coin of environmental engineering today. The
global climate change, the loss of ecological biodiversity, and the frequent
environmental disasters are urging the scientists and engineers to gear forward
toward a more visionary future with respect to innovations and challenges. In this
paper the author deeply addresses the various technologies of remediation of
industrial and automobile exhausts for environmental management. Global sci-
entific orders are in a state of deep challenges, unending vision, and deep
comprehension. The future of environment is immensely dismal. This paper
opens up new windows of scientific innovation and scientific instinct in the
field of environmental management in decades to come.
Keywords
Industrial · Automobile · Exhausts · Vision · Environment · Sustainability
Introduction
Environmental management and environmental engineering science are today in the

path of immense scientific vision and deep regeneration. Scientific fortitude and
scientific ingenuity in application of environmental engineering tools to tackle global
air pollution issue is in a dismal state. Industrial and automobile exhausts are the
major pollutants of modern civilization today. Human scientific vision in air and
water pollution control is witnessing immense and drastic challenges. Scientific
endeavor needs to be readdressed and revamped as science and engineering of
environmental protection surges forward. Technology and engineering science has
today few answers to the marauding crisis of global climate change. In the similar
vein, industrial wastewater treatment and drinking water treatment are the burning
issues and scientific enigma of modern human civilization. In this paper, the authors
pointedly focus on the scientific success and the scientific subtleties of the applica-
tion of environmental engineering tools to protection of global environment. The
advancement of engineering science, the needs of human society, and the futuristic
vision of environmental engineering science will all lead a long and visionary way in
the true emancipation of environmental sustainability. The success of science of
environmental protection is enumerated in this chapter. Environmental management
and true realization of environmental sustainability are the two opposite sides of the
visionary coin today. Today, global environment is faced with the monstrous issue of
water shortage and groundwater heavy metal contamination. Arsenic groundwater
contamination is a veritable curse to modern day human civilization and the vast
scientific research pursuit. This chapter also is a veritable eye-opener to the scientific
difficulties, the scientific barriers, and the vast scientific profundity in the control of
industrial and automobile exhausts. This entire chapter opens up new doors of
innovation in the field of environmental management also. Today environmental
34 Remediation of Industrial and Automobile Exhausts for Environmental. . . 891
management is the need of the hour. Human scientific endeavor in environmental

management today stands in the midst of vision and deep scientific fortitude. The
challenge and the vision of the science of environmental management are today
surpassing vast and versatile visionary frontiers. This paper opens up new chapters in
the scientific research pursuit in both environmental engineering and environmental
management.
The Aim and Objective of this Study
Science and technology are vast avenues of vision and emancipation today. Envi-
ronmental engineering and industrial wastewater treatment are in the midst of deep
scientific introspection and vast scientific vision. The aim and objective of this study
goes beyond scientific imagination and replete with scientific profundity and vast
scientific acuity. Today the scientific world is faced with immense environmental
issues such as global climate change and frequent environmental disasters. Air
pollution and industrial exhausts are the causes of grave concern as science and
engineering surges forward toward a newer visionary realm. In the similar vein,
environmental management should be the hallmark of deep scientific profundity in
modern day human civilization. In this paper, the authors rigorously point toward the
need of environmental engineering tools to confront the emission of industrial and
automobile exhausts with the sole objective of furtherance of science and engineer-
ing of environmental protection. Environmental sustainability and environmental
engineering science are moving toward newer knowledge dimensions as science and
engineering surges forward. Industrial wastewater treatment and drinking water
purification are the other cornerstones of this well-researched treatise. Today arsenic
and heavy metal groundwater contamination are destroying the scientific landscape
of immense vision and scientific might. In this chapter, the authors clearly and
poignantly depict the vast scientific vision behind the application of engineering
tools in tackling industrial and automobile exhausts (Najjar 2011). Human scientific
ingenuity and vast scientific foresight are the necessities of modern science and
research pursuit today. This chapter veritably opens up newer scientific innovations
and newer scientific insights in the field of air and water pollution control with the
sole purpose of furtherance of science and engineering (Najjar 2011).
Sources of Classification of Industrial and Automobile Exhausts

and Disposal
Environmental pollution control and air pollution control today needs to be

re-envisioned and restructured with the passage of scientific history and time.
Transportation is a major component of modern civilization’s scientific progress.
Transportation is also the heart of modern industrial systems which involves
resources and means for their transformation, pumps out products, and provides an
inseparable link between the different parts of industrial systems as a vital and
veritable part of commercial activities. Transportation is also the mobile source of

major anthropogenic contribution to environmental protection (Najjar 2011). The
sources of industrial air pollution are calcium carbide industry; carbon black indus-
try; cement industry; brick kilns; copper, lead, and zinc smelting units; coal mines;
diesel generator sets; vehicular exhaust emission; and a host of other pollutants
(Najjar 2011). Exhaust gas is a major component of motor vehicle emissions (and
from stationary internal combustion engines) which can include (1) crankcase blow-
by and (2) evaporation of unused gasoline (Najjar 2011). Motor vehicle emissions
contribute to air pollution and are a major ingredient in the creation of smog in large
cities. Scientific vision and vast scientific acuity should be the targets of scientific
endeavor in air pollution control today. Science of environmental protection should
start a newer beginning and new technologies, and newer innovations should be
deeply envisioned (Najjar 2011).
Toxicity of Exhausts and their Release to Environment
Generally an exhaust gas is a gas emitted through a combustion process. The exhaust
gases comprise of many different gases: nitrogen, carbon dioxide, water, and oxygen
(Najjar 2011). Though some are harmless, there are a few that are harmful and are
considered major pollutants. Ecological engineering and environmental protection
are today linked by an unsevered umbilical cord. Urban smog is a dark yellow or
brown haze that builds up in a large stagnant air mass and hangs over populated areas
on calm hot summer days (Najjar 2011). Smog is made of mainly ground-level
ozone, but it also contains numerous other chemicals including carbon monoxide,
particulate matter such as soot and dust, and volatile organic compounds such as
benzene, butane, and other hydrocarbons. The main source of both nitrogen oxides
and hydrocarbons is the motor vehicles. Hydrocarbons and nitrogen oxides react in
the presence of sunlight in hot calm days to form ground-level ozone, which is the
primary component of smog. Ozone irritates the eyes and damages the air sacs in the
lungs where oxygen and carbon dioxide are veritably exchanged, causing eventual
hardening of soft and spongy tissues. Technology and engineering science of
environmental protection should thus be re-envisioned as regards health effects
and more robust pollution control strategies (Najjar 2011).
Possibilities of Remediation and Deactivation of Exhausts
Catalytic converters are used to reduce emissions in cars (Najjar 2011). Actually an
automotive catalyst uses precious metals: platinum, rhodium, and palladium. When
toxic substances (carbon monoxide, hydrocarbons, and nitrogen oxides) are in
contact with these metals, they are immediately converted. Today ecological engi-
neering and water process engineering are on the path of newer scientific rejuvena-
tion (Najjar 2011). Many nations throughout the world depend on oil for energy
uses and sustainable development, hence import all of its oil and gas needs.
Thereby, consequent harmful and disastrous effects on the environment, such as

global warming, ozone, smog, and acid rain, may result from the gases emanating
from fossil fuel combustion (Najjar 2011). Biofuel technologies are another avenue
of reducing exhaust gas emissions. Increased use of biomass-based renewable fuel
can be another visionary opportunity for minimizing air polluting emissions (Najjar
2011). While conventional biofuel is derived from corn starch, advanced biofuel is
produced from other renewable biomasses such as (1) cellulose, hemicelluloses, and
lignin, (2) sugar and nonsugar starch, (3) waste material such as agricultural crop,
(4) planted trees and tree residues, (5) animal wastes, (6) algae, and (7) separated
food wastes (Najjar 2011). This is a major avenue of scientific research pursuit today.
Plasma-assisted catalyst for nitrogen oxides remediation from lean gas exhausts is a
major scientific endeavor today (Najjar 2011).
Significant Scientific Endeavor in the Field of Air Pollution Control

of Industrial and Automobile Exhausts and Industrial Wastewater
Treatment
Air pollution control and industrial wastewater treatment today stand in the midst of
vast vision and scientific fortitude. Environmental calamities and global climate
change are today challenging the scientific firmament and veritably opening up
new doors of scientific innovation and scientific instinct in decades to come.
Research and development initiatives in the field of water science and air pollution
control are ushering in a new era in the field of scientific emancipation and techno-
logical validation. Validation of science and engineering are the utmost need of the
hour as human civilization surges forward. Drinking water purification, desalination,
and industrial wastewater treatment are the needs of human society today. In this
chapter, the author pointedly focuses on the vast scientific success, the scientific
subtleties, and the deep scientific ingenuity in the field of air pollution control,
remediation of industrial and automobile exhausts, and the vast world of scientific
validation.
Rajendran et al. (2003) deeply discussed with cogent and lucid insight microbes
in heavy metal remediation. Technological candor, the deep scientific vision and the
vast world of scientific validation are the pillars of science today. This treatise is a
vast scientific discernment and a deep scientific vision in the field of heavy metal
remediation. Heavy metal contamination due to natural and anthropogenic sources is
a global environmental concern. Drinking water treatment and industrial wastewater
treatment today stand in the midst of vision and deep scientific ingenuity. Release of
heavy metal without proper treatment poses a deep and significant threat to public
health and hygiene because of its persistence, biomagnification, and accumulation in
food chain (Rajendran et al. 2003). Human scientific endeavor and research and
development initiatives in water technology are today ushering in a new era in
science and engineering. Non-biodegradability and sludge production stand as a
major scientific impediment in human civilization today (Rajendran et al. 2003).
Recent advances have been made in understanding metal-microbe interaction and
their application for metal accumulation. Human scientific progress in biochemical

engineering and environmental science thus needs to be re-envisioned as engineer-
ing science and technology moves from one visionary paradigm toward another
(Rajendran et al. 2003). There is a greater need of metal bioremediation. The
technology of bioremediation is highly advanced today and surpassing vast and
versatile scientific boundaries. Greater awareness of the ecological effects of toxic
metals and their biomagnifications through food chain as well as environmental
disasters such as mercury pollution in Minamata, Japan, has vastly prompted a
demand for decontamination of heavy metals in the aquatic environments
(Rajendran et al. 2003). The challenge and vision of global research and develop-
ment initiatives in water pollution control are immense and pathbreaking. Essential
metals are required for enzyme catalysis, nutrient transport, protein structure, charge
neutralization, and the need for control of osmotic pressure. A number of heavy
metals are required as micronutrients in plants (Rajendran et al. 2003). They act as
cofactors as part of prosthetic groups of enzymes which are involved in a wide
variety of metabolic and scientific pathways (Rajendran et al. 2003). Metal concen-
trations have been linked to birth defects, cancer, skin lesions, retardation leading to
disabilities, liver and kidney damage, and a host of other health issues. This paper
pointedly focuses on the scientific success and the scientific ingenuity in the appli-
cation of microbes in bioremediation. Human scientific and technological innova-
tions in bioengineering are today vast and versatile scientific boundaries. The world
of science and engineering is today in the midst of vision and vast scientific
articulation. The authors in this paper discuss conventional methods of heavy
metal removal from soil and water, microbes for metal remediation, bioremediation
techniques, mechanisms for metal tolerance, genetic engineering for metal remedi-
ation, biosorption, immobilization for metal remediation, and plant-microbe inter-
action in metal remediation (Rajendran et al. 2003). The authors in this treatise
deeply comprehend the success of biochemical engineering and biochemistry in
metal remediation (Rajendran et al. 2003). Air pollution control is a vast area of
scientific endeavor today. Human scientific challenges and the vast scientific genre
in bioengineering and water technology are deeply addressed in this paper.
Shannon et al. (2008) deeply discussed with lucid and cogent insight science and
technology for water purification in the coming decades. One of the enigmatic issues
of scientific endeavor and scientific civilization today is inadequate access to clean
water and sanitation. Science and engineering of water purification is today ushering
in a new era in the field of global water shortage issues. Problems with water are
expected to grow worse in the coming decades, with water shortage occurring
globally, even in water-rich regions throughout the world (Shannon et al. 2008).
Addressing these issues calls out for a tremendous effort to be conducted to identify
robust new innovations of purifying water at a low cost and with less energy while at
the same time minimizing the use of chemicals and preventing the impact on
environment. The vast many problems worldwide associated with the lack of
clean, fresh water are vastly well known: 1.2 billion people lack proper access to
safe drinking water, 2.6 billion have little or no sanitation, and millions of people die
annually – 3900 children a day – from diseases transmitted through impure and
unsafe water (Shannon et al. 2008). Human mankind’s immense scientific prowess,
the futuristic vision of water technology, and the imminent needs of pure drinking
water will go a long and visionary way in the true emancipation of water process
engineering today. Today chemical process engineering and environmental engi-
neering science are in the avenue of vast and versatile scientific ingenuity. Technol-
ogy and engineering have few answers to the monstrous issue of global water
scarcity and groundwater contamination. The authors in this paper deeply discussed
the concepts of disinfection, decontamination, reuse, and reclamation and desalina-
tion. The need for global water research and development initiatives is elucidated in
details in this paper (Shannon et al. 2008). The overarching goal of this research
paper is to target the needs of water process engineering, the technological vision,
and the vast scientific profundity (Shannon et al. 2008).
The US Environmental Protection Agency Report (2010) deeply discussed, with
immense scientific conscience, green remediation best management practices and
clean fuel and emission technologies for site cleanup (United States Environmental
Protection Agency Report 2010). Mankind’s immense scientific prowess, man’s vast
scientific vision, and the futuristic vision of basic human needs will lead a long and
visionary way in the true emancipation of environmental management and environ-
mental sustainability (United States Environmental Protection Agency Report
2010). This report outlines the Agency’s policy for evaluating and minimizing the
environmental footprint of activities undertaken when cleaning up the contaminated
site. Human scientific regeneration and vision today stand in the midst of deep crisis.
Cleanup of hazardous waste sites can involve significant consumption of gasoline,
diesel, or other fuels by mobile and stationary sources. This report with deep
scientific conscience discussed operations and maintenance, advanced diesel tech-
nologies, alternative fuels and additives, and the wide domain of alternative vehicles.
The need of remediation technologies in industrial and automobile exhausts is today
immense and pathbreaking. Mankind’s immense scientific challenges in air pollution
technologies and the innovations behind it are deeply discussed in this report (United
States Environmental Protection Agency Report 2010).
Bioremediation of contaminated soils and its in situ and ex situ techniques are the
challenges of science and engineering today. For the treatment of contaminated soils,
the application of biotreatment is growing at a rapid pace today. Scientific progress,
scientific acuity, and deep scientific farsightedness are the imminent necessities of
bioremediation today. In this chapter, the authors deeply discussed with cogent
insight the success, the ingenuity, and the fortitude behind scientific emancipation
of remediation of industrial exhausts.
The US Environmental Protection Agency Report (1998) deeply discussed with
vast insight an analysis of composting technologies as an environmental remediation
technique. The composting process is currently viewed primarily as a waste man-
agement method to stabilize organic waste such as manure, yard trimmings, munic-
ipal biosolids, and organic urban wastes (United States Environmental Protection
Agency Report 1998). Human civilization and human scientific endeavor today
stand in the midst of deep scientific vision and vast forbearance. This report
summarizes the available information on the use of compost for managing hazardous
waste streams and widely investigates possible future recommendations of remedi-

ation technologies (United States Environmental Protection Agency Report 1998).
A deep scientific discernment on cross-media transfer of contaminants during the
implementation of various bioremediation technologies is addressed in details in this
report. Groundwater remediation and bioremediation are the absolute needs of the
human civilization and the human scientific endeavor today. Composting is a
managed system that uses microbial activity to degrade raw organic materials,
such as yard trimmings, so that the end product is relatively stable, reduced in
quantity, and free from offensive odors (United States Environmental Protection
Agency Report 1998). Technology and engineering science of bioremediation is
today attaining visionary heights as global concerns for environment aggravate. This
report opens up new ideas of scientific innovation and scientific instinct in the field
of composting technology and bioremediation (United States Environmental Pro-
tection Agency Report 1998).
The Central Pollution Control Board Report (2010), India, discussed with deep
and cogent insight the study of the exhaust gases from different fuel-based vehicles
for carbonyls and methane emissions. Air pollution is caused by a number of
pollutants evolved from various sources. Under air pollution control strategy, the
detailed analysis and assessment of all the pollutants having detrimental effects on
human health and environment are required (Central Pollution Control Board, India
Report 2010). Thus the need of this vast scientific vision and scientific endeavor. A
developing country like India today is in the midst of a vast scientific crisis and
technological vision. The authors firstly did a comprehensive literature review and
then did a detailed methodology and after that delineated and discussed future
recommendations. Scientific progress, the needs for air pollution control strategy,
and the visionary technologies are the veritable torchbearers of environmental
sustainability today. Environmental sustainability and infrastructural development
both today stand in dire straits and vast scientific catastrophe. Technology and
engineering science needs to be re-envisioned and thoroughly addressed with the
passage of scientific history and time. The success of human scientific ingenuity in
air pollution control strategies is elaborated deeply in this report (Central Pollution
Control Board, India Report 2010).
The International Energy Agency Report (2008) did a comprehensive study of
carbon dioxide capture in the cement industry. The knowledge dimensions, the vast
futuristic vision of air pollution control, and the human scientific needs will all lead a
long and visionary way in the true emancipation of environmental sustainability
today. Today air pollution control is a visionary parameter of scientific endeavor in
environmental protection. The cement industry is one of the world’s largest indus-
trial sources of carbon dioxide emissions accounting for more than 6% of global
emissions from the use of fossil fuels. Scientific validation and the vast technological
vision are the necessities of research and development initiatives in air pollution
control today. Human mankind today stands in the midst of deep scientific discern-
ment and definite vision (International Energy Agency Report 2008). Over the years,
the cement industry has substantially reduced emissions of carbon dioxide per tonne
of cement by improving energy efficiency, replacing fossil fuels with wastes which
can sometimes be regarded as “carbon neutral,” and by increasing the use of

additives in the cement product (International Energy Agency Report 2008). Scien-
tific rejuvenation and deep scientific understanding are the hallmarks of human
civilization today. In this report, the author deeply comprehends the effect of
greenhouse gas emissions in cement industry. The report describes cement plants
and the global cement industry, reviews the carbon dioxide capture processes,
evaluates the performance and economics of cement plants, discusses retrofitting
carbon dioxide capture, and vastly identifies vast research and development needs.
Today the world of engineering and technology is in the avenue of a vast scientific
regeneration. This report is a case study of the human scientific progress in air
pollution control strategies in cement industries (International Energy Agency
Report 2008).
Environmental management today stands in the midst of deep scientific intro-
spection and vast scientific foresight. Today is the age of nanotechnology and
nanomaterials. Nanomaterials or smart materials are the technological innovations
of modern science and modern civilization. Environmental analysis and environ-
mental protection are today linked by an unsevered umbilical cord.
Aghabozorg and Hassani (2017) discussed with vast insight the removal of
pollutants from the environment using sorbents and nanocatalysts. The authors in
this well-researched chapter discussed the removal of sulfur compounds from fuels,
elimination of heavy metals from wastewater, and separation of the dangerous
radionuclides from liquid nuclear wastes (Aghabozorg and Hassani2017). Pollutants
are generally waste materials of different forms that veritably effect the balance in
the environment. Industrial modernization and progress over the years have resulted
in a burgeoning environmental impact. Chemical and petroleum industries introduce
many pollutants into the surrounding environment (Aghabozorg and Hassani 2017).
The authors in this chapter delineated with precision the removal of sulfur com-
pounds from fuels. There are different kinds of sulfur compounds in hydrocarbon
fuels, owing to new environmental regulations. Thus the status of the environment is
immensely dismal. Human civilization thus is in a state of immense distress
(Aghabozorg and Hassani 2017). Many research and development forays have
been performed about the removal of sulfur compounds from the middle distillate
fraction, such as gasoline, jet and diesel fuels, and kerosene, to produce clean fuels.
In this aspect, hydrodesulfurization is an important catalytic process that has been
developed for decreasing the sulfur contents in engine fuels to less than 2 ppm
(Aghabozorg and Hassani 2017). So here the authors stressed on the importance of
technological innovations in sulfur removal. The other upshot of this process is the
elimination of heavy metals from wastewater. Heavy metals, such as mercury,
arsenic, lead, cadmium, and chromium, can contaminate the environment owing to
their toxicity. The unit operation in chemical engineering touched upon is adsorption
(Aghabozorg and Hassani 2017). The other areas of this scientific endeavor are the
separation of the dangerous radionuclides from liquid nuclear wastes (Aghabozorg
and Hassani 2017). Radiological contamination is the presence of radioactive mate-
rials within solids, liquids, or gases where their presence is not desired. This
contamination rises to an immense health hazard and a burning issue of
environmental engineering science. Human scientific endeavor in environmental

protection today is in a state of immense catastrophe and deep comprehension
(Aghabozorg and Hassani 2017). Accidental release of radioactive elements (such
as uranium, cesium, and strontium, which are serious pollutants) to the air leads to a
massive deposition of these metals into the soil, vegetation, and water. Thus envi-
ronmental protection is the utmost need of the hour. In this chapter, the author with a
deep precision and insight delineates pollutant removal technologies with a clear
view of furtherance of science and engineering (Aghabozorg and Hassani 2017).
Azzaza et al. (2017) in a phenomenal research endeavor discussed nanomaterials
for heavy metal removal. Toxic metals (called heavy metals) are a part of the earth’s
crust. They occur in rocks and are predominantly distributed in the environment
(soil, water, and air) (Azzaza et al. 2017). The challenge and the vision of engineer-
ing science and technology are today far-reaching and surpassing the vast and
versatile scientific frontiers. Environmental engineering is today a frontier science
today. Human scientific progress in environmental engineering science needs to be
re-envisioned and revitalized as civilization surges forward. In order to make the
environment healthier for human beings, contaminated water streams and contam-
inated lands need to be rectified to free them from heavy metals and free elements.
The types of adsorbents used in such a case are carbon-based nanomaterials,
activated carbon, carbon nanotubes, graphenes, metal-based nanomaterials, and
nanosized metal oxides (Azzaza et al. 2017). Human scientific fortitude and
human scientific farsightedness in the field of research forays in environmental
engineering are today ushering in a new eon of vision and might. The authors in
this chapter deeply ponder upon the newer applications of nanomaterials in heavy
metal removal and environmental protection in a broader sense (Azzaza et al. 2017).
Visionary Scientific Endeavor in the Field of Environmental

Management
Environmental management is today the utmost need of human civilization today.

The state of global environment is in a state of immense scientific distress and replete
with scientific barriers. Yet science and engineering of environmental protection is
today surpassing vast and versatile scientific frontiers. In the similar manner, envi-
ronmental management is a frontier science today. The need for environmental
management is immense for human society today. Human civilization today stands
in the midst of immense scientific barriers and deep scientific vision. Environmental
sustainability and environmental protection are in the process of vast scientific
regeneration. In this section the author deeply ponders on the vast scientific research
and vast scientific ingenuity in the application of environmental management in
human scientific progress. Technology and science are too ebullient and visionary in
the path toward scientific emancipation today. Scientific endeavor in the field of
environmental management needs to be re-envisioned and restructured as science
moves toward a newer era of environmental engineering emancipation.
Rusko and Prochazkova (2011) discussed with deep and cogent insight the
solution to the problems of the sustainable development management. Human
scientific insight in environmental management is today in the path of immense
rejuvenation. This paper shows that environment is one of the basic public assets of a
human system, and it must be therefore specially protected and re-envisioned.
According to the present scientific world, the sustainability science is necessary
for all human systems, and it is absolutely necessary to invoke the sustainable
development principles in all human assets and all human genres (Rusko and
Prochazkova 2011). The vision of Dr. Gro Harlem Brundtland, former Prime
Minister of Norway today, needs to be restructured and re-envisaged as civilization
moves forward. Sustainable development is understood as a development that
veritably does not erode ecological, social, or political system on which it depends,
but it explicitly approves ecological limitation under the economic activity frame,
and it has full comprehension for support of vast human needs. This well-researched
paper summarizes the results of the systematic study of the environment in the last
30 years (Rusko and Prochazkova 2011). Social sustainability and economic sus-
tainability are today the cornerstones of scientific research pursuit in environmental
sustainability and environmental protection today. The vision of science and tech-
nology is today groundbreaking and too effervescent with the march of environ-
mental management. This paper outlines the tools, methods, and techniques used to
solve the environment problems and the tasks of executive governance in the
environmental protection segment (Rusko and Prochazkova 2011). The environment
itself is a system of systems that, from the viewpoint of human existence and
development, is a part of the superior system of systems, the human system. Based
on the recent cognition, sustainable development is not only related to the environ-
ment but also to the entire human system and its basic assets (i.e., public assets) on
which the human lives are dependent (Rusko and Prochazkova 2011). Sustainable
development, infrastructural development, and environmental sustainability are the
necessities of human civilization today. This paper opened a new chapter in the field
of sustainable development management along with a deep comprehension of
environmental sustainability.(Rusko and Prochazkova 2011)
The US Department of Energy (2016) delved deep into the basic research needs
for environmental management. The upshot of the paper detailed waste stream
characterization, transformation, and separations, waste forms, contaminant fate
and transport in geological environments, exploitation of complex speciation and
reactivity far from equilibrium, understanding of chemical and physical processes at
interfaces, harnessing of physical and chemical processes to revolutionize separa-
tions, mechanics of materials degradation in environment, predictive understanding
of subsurface system behavior and response to perturbations, and transformative
research capabilities (Office of Science, Department of Energy, USA Report 2016).
Human scientific progress in environmental management is in the process of new
scientific regeneration. Technology and engineering science have few answers to the
scientific difficulties and scientific travails of environmental management (Office of
Science, Department of Energy, USA Report 2016). The authors deeply delve into
the success of the science of environmental management. Human civilization today
stands in the midst of deep scientific comprehension and vast vision of its own. This
report vastly opens a new chapter in the field of environmental management and
environmental sustainability with a clear scientific conscience and clear scientific
profundity. Scientific discernment and deep scientific vision are all leading a long
and visionary way toward the true emancipation of environmental management.
Sustainable development is showing a new path in the domain of environmental
engineering science. The management of environment and the vast research needs in
its true realization are the hallmarks of this research endeavor (Office of Science,
Department of Energy, USA Report 2016).
Ahmad et al. (2009), with immense lucidity, discussed environmental management
system and sustainability. Technological validation and deep scientific validation are
the research needs in environmental management systems today (Ahmad et al. 2009).
To check rapidly the deteriorating environmental conditions, many management tools
are being used in different industries. Technology and engineering science are the two
huge pillars with a definite vision of its own. Today the corporate world is highly
interested in the application of environmental system in its industries. Environmental
science and environmental sustainability are the other areas of research need today.
There is a strong need to check how these environmental management systems are
rendering environmental management services. This paper opens a new window in the
framework for strategic sustainable development and strategic life cycle management
(Ahmad et al. 2009). Scientific candor, vast scientific profundity, and the needs of
human society are today ushering in a new era in the field of strategic life cycle
management. The use of management tools in the application of sustainability to
modern society is deeply elaborated in this chapter (Ahmad et al. 2009).
Kumar and Katoria (2013) discussed with deep and cogent farsightedness air
pollution and its control measures. An important parameter in environmental man-
agement system is the vast domain of air pollution control and industrial water
pollution control. In this paper, the authors deeply pronounce the success of scien-
tific vision and vast scientific ingenuity in the application of air pollution control
measures. Air pollution is basically the foreign material in the air, can be man-made
or occur naturally, and is concentrated in area where people are predominantly
present. Pollution is injurious to health and its prevention places an economic burden
on the human mankind. The aim of this study is to understand the innovation activity
in technological and scientific domain and the different ways to observe patterns in
relation to diffusion of innovation in different jurisdictions. The authors emphasize
on prominent Indian company active in air pollution control measures in innovative
technology business and research and development initiatives. Scientific progress in
air pollution control is today in the state of immense scientific regeneration and deep
vision (Kumar and Katoria 2013). This paper highlights the various countries on
priority list of innovative technologies for the protection and exploitation of devel-
oped technologies. Human scientific endeavor is today in the state of immense
scientific regeneration and deep revival. Air pollution control stands in the midst
of vast and wide scientific revival (Kumar and Katoria 2013).
The World Bank Report (1996) vastly comprehends the standards and technol-
ogies for controlling emissions. The report deeply delineates emission standards
and regulations in many developed and developing countries, quantification of

vehicle emissions, vehicle technology for controlling emissions, controlling of
emissions from in-use vehicles, and fuel options for controlling emissions.
Because of their versatility, flexibility, and low initial cost, motorized road vehicles
overwhelmingly dominate the markets for passenger and freight transport through-
out the world (The World Bank Report 1996). Thus the need of stringent emission
control regulations and stringent restrictions. The futuristic vision of air pollution
control, the vast technological vision, and the deep scientific profundity will all
lead a long and effective way in the true emancipation of environmental legisla-
tions today. This is a comprehensive report which elucidates on the present and
future of environmental legislations globally. In all but the poorest developing
countries around the world, economic growth has ushered in an era of increase in
the number and use of motor vehicles (The World Bank Report 1996). Techno-
logical subtleties and deep engineering succor are the cornerstones of scientific
validation today. A deep scientific thought and a vast scientific understanding are
the utmost need of the hour as air pollution control technologies move from
one visionary paradigm over another (The World Bank Report 1996). Apart from
the other vehicles, motorized road vehicles will retain their overwhelming presence
in road transport. This handbook presents a state-of-the-art review of vehicle
emission standards and testing procedures and vastly delineates worldwide expe-
rience with vehicle emission control innovations and its application in both
industrialized, developed and developing countries throughout the world. The
overarching goal of this handbook and report is to underpin the World Bank’s
overall objective of promoting transport development that is vastly environmen-
tally sustainable and totally replete with scientific vision and scientific clarity
(The World Bank Report 1996).
Seetharam (2014) discussed with immense foresight automobile exhaust pol-
lution and its effective control. With increase of standard of living and growing
need for faster road communication, the number of automobiles has been steadily
increasing and also pollution from them. The exhausts from them are causing
serious threats to public health and hygiene and the quality of life. In addition poor
maintenance of roads, adulteration of fuels, improper maintenance of vehicles, and
heavy vehicular inflow also vastly aggravate the problem (Seetharam 2014). The
pace of urbanization resulting in an enormous increase in population and industrial
activities has resulted a huge demand of traffic. The factors influencing emissions
are air-fuel ratio, spark timing, carburetion, and surface-to-volume ratio of the
combustion chamber. Human scientific research pursuit and scientific acuity are
the needs of modern day human civilization. Remediation of industrial and
automobile exhausts is the immediate need of scientific vision and profundity
today (Seetharam 2014). The sources of automobile emissions are exhaust emis-
sions, evaporative emissions, carburetor emissions, and crankcase emissions. Thus
the need of intense scientific innovations (Seetharam 2014). The pollution control
measures are fuel change, engine modification, stratified charge engine, reduction
of carbon monoxide emissions, decrease of NOx emissions, and reduction of
traffic jams in metropolitan cities around the world. The author in this paper
pointedly focuses on the vast scientific success, the immediate needs of scientific
farsightedness, and the vast scientific vision of air pollution control (Seetharam
2014).
Human scientific vision and deep scientific fortitude are today in the path of
newer regeneration. Global concerns for environment are ever growing due to the
severities of climate change, loss of ecological biodiversity, and frequent environ-
mental catastrophes. Technology, engineering, and science have few answers to the
marauding issue of water shortage, air pollution, and industrial wastewater treat-
ment. Thus here comes the need of environmental management and environmental
sustainability. In this chapter, the authors rigorously delineate the vision of environ-
mental management systems and its application to human society and human
scientific progress (Palit 2017a, b; Hashim et al. 2011).
Environmental and Energy Sustainability and the Vast Vision

for the Future
Environmental and energy sustainability are the needs of human society and
modern science today. Sustainable development, infrastructural development, and
the futuristic vision of scientific validation will all lead a long and visionary way in
the true emancipation and the true realization of environmental engineering tech-
niques and environmental sustainability. The vision for the future in the implemen-
tation of sustainability science to human society needs to be redrafted and
reorganized with the passage of scientific history and visionary timeframe. Air
pollution control techniques and control of industrial and automobile exhausts are
the utmost needs of human society today. This paper deeply comprehends the
scientific success, the vast scientific profundity, and the imminent scientific needs
of human civilization today. The perspectives of science and engineering are vast
and versatile today. In the similar vein, scientific discernment and scientific per-
ception in the field of environmental protection need to be re-envision with human
scientific progress. Water purification technologies and industrial wastewater treat-
ment are the other needs of human society today. Zero-discharge norms, vast
environmental regulations, and the deep scientific acuity are the veritable torch-
bearers toward a true realization of environmental sustainability. The glowing
vision of Dr. Gro Harlem Brundtland, former Prime Minister of Norway on the
domain of “sustainability science,” needs to be readdressed and re-envisioned as
global climate change crisis is tackled. Scientific succor and deep scientific subtle-
ties are the necessities of inventions and vast innovations today. The authors in this
treatise deeply enumerate the scientific success, the scientific needs, and the vast
scientific discernment in the field of air and water pollution control technologies
today. Man’s immense scientific prowess, human mankind’s vast scientific needs,
and the need for scientific validation will be the torchbearers of the future of science
and technology. This paper goes beyond scientific imagination and scientific
barriers in addressing the success of scientific and technological validation today
(Palit 2015, 2016a, b).
Future Research Trends and Future Recommendations
The science of environmental engineering and applied science are today in the midst of
deep scientific discernment and vast scientific foresight. Scientific research forays in
industrial and automobile exhaust remediation need to be readdressed and revamped as
human civilization moves forward. Today environmental science and engineering are
huge colossus with a vast and definite vision of its own. Technology has few answers to
the burning issue of groundwater heavy metal contamination. Arsenic groundwater
contamination is a scientific enigma in developed and developing countries throughout
the world (Cheryan 1998). Big cities and metropolis throughout the world are faced
with the difficult situation of automobile and industrial exhausts which are destroying
the environment (Cheryan 1998). The vision of science, the needs of environmental
engineering, and the futuristic vision of air pollution control will go a long and effective
way in the true realization and true emancipation of environmental sustainability.
Future research trends should be targeted toward scientific emancipation in environ-
mental management and sustainable development. Today nanotechnology and nano-
materials are integrated with every branch of scientific endeavor. This also should be
the future recommendations of this study. Human scientific vision will only be realized
if the basic human needs such as water and energy are met. Here comes the importance
of energy and environmental sustainability. Human mankind’s immense scientific
determination, the innumerable technological challenges, and the needs of sustainable
development will surely open new windows of scientific innovation in decades to come
(Cheryan 1998).
Conclusion and Future Perspectives
Science and technology are the two huge colossuses with a definite and vast vision of
its own. Environmental engineering science and air pollution control today stand in
the midst of deep scientific comprehension and acuity. Future perspectives in
scientific research pursuit in environmental pollution control should be targeted
toward innovations and scientific instinct. Global climate change is today challeng-
ing the scientific firmament of vision and foresight. The science of sustainability
today stands in the midst of deep scientific introspection and vast scientific chal-
lenges. Human scientific struggle in the field of environmental protection is highly
challenged today. Technology and engineering science in such a crucial juncture of
human history needs to be restructured and readdressed as human mankind moves
from one visionary paradigm to another. Global water research and development
initiatives in the similar manner need to be revamped as science and technology
surges forward. Industrial wastewater treatment and drinking water treatment should
be equally revitalized and reorganized with the march of science. In this paper, the
author elucidates with deep and cogent insight the need for environmental sustain-
ability and environmental protection in tackling the intricacies of scientific research
pursuit. The challenge and vision of environmental engineering, chemical process
engineering, and applied science are in the process of newer scientific regeneration.
The authors in this treatise deeply fulfill the utmost need of scientific literature and
scientific initiatives in tackling global environmental engineering issues. Future
recommendations and future flow of scientific thoughts should be vastly targeted
toward the provision of basic human needs, the needs of energy security, and the vast
world of research and development initiatives in water science and technology.
Energy sustainability is another vast avenue of scientific endeavor today. Human
scientific challenge in this area is immense and groundbreaking. Energy security and
energy sustainability are today connected by an unsevered umbilical cord. This
treatise opens up new scientific understanding and the vast scientific vision in energy
sustainability issues of human society. Environmental management is today another
big and enigmatic scientific issue. Academic and scientific rigors in environmental
management are deeply elucidated in this paper. The authors in this paper vastly
comprehend the basic needs of human society today such as water, energy, and
food. The challenge and the vision of scientific research pursuit in environmental
management and environmental pollution control stand as the major pillars of this
entire paper.
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Management of Residues from Air Pollution
Control Systems 35
Christof Lanzerstorfer
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908
Air Pollution Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908
General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908
Air Pollution Control Tasks and Residues Thereof . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908
Residues from Air Pollution Control in Major Industry Sectors . . . . . . . . . . . . . . . . . . . . . . . . . . . 911
Enrichment of Volatile Elements in the Off-Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 913
Ways of Utilization of Air Pollution Control Residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
Use as Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
Direct Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 916
Treatment of Residues for Recycling or Utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
Use of Residues in Another Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 919
New Ways of Utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 920
Landfill . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
Backfilling in Mines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
Solidification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
Abstract
This chapter gives an overview of the residues generated in various industrial air
pollution control processes. After summarizing the amount of resulting residues
in various industries the current ways of utilization, treatment, and disposal of
these residues as well as actual developments and future prospects are reviewed.
C. Lanzerstorfer (*)
University of Applied Sciences Upper Austria, Wels, Austria
e-mail: Christof.Lanzerstorfer@fh-wels.at

https://doi.org/10.1007/978-3-319-73645-7_153
908 C. Lanzerstorfer
Keywords
Air pollution control · Waste hierarchy · Reduce · Reuse · Recycle · Energy use ·
Disposal · Economical solution · Emission abatement
Introduction
Air pollution control (APC) systems have become important in all industrial pro-
duction plants. The pollutants previously emitted to the atmosphere are now sepa-
rated from the off-gas and remain as residues from the APC systems.
In the selection of an APC process the most important requirement is to achieve
compliance with the legal emission limits. Another important target is to find the
most economical solution for the given emission abatement task. In the economic
evaluation of different processes, the costs incurred for the treatment or disposal of
the remaining residues can play an important role (Quina et al. 2011; Karatepe
2000). From an environmental point of view, the different levels of the waste
hierarchy, reduce, reuse, recycle, energy use, and disposal in descending order
should also be taken into account.
Air Pollution Control
General
APC processes are typically classified into two main categories, wet processes and
dry processes. In dry processes no liquid effluent from the process exists, whereas in
wet processes a wastewater stream is usually generated. Under certain conditions
some wet processes can be operated without discharging wastewater.
Table 1 provides an overview of important APC processes for the main pollutants
as well as the types of residues produced.
Besides the type of pollutants to be separated and the off-gas parameters the
selection of an APC process has also to consider several circumstances with respect
to residues:
• The possibility of discharging wastewater

• Local proximity of potential customers for residual products
• Local proximity of potential treatment facilities for APC residues
• Cost and local proximity of landfills
Air Pollution Control Tasks and Residues Thereof
De-dusting
In a dry de-dusting process, the composition of the separated dust is usually the
same as the composition of the emitted dust. However, there are also combined
35 Management of Residues from Air Pollution Control Systems 909
Table 1 Important off-gas cleaning processes and remaining residues

Pollutant Process/equipment Residues
Particles, dust Cyclone, inertia separator Dry dust
Electrostatic precipitator (ESP) Dry dust
Filter (pulse jet filter, baghouse, filter Dry dust
with ceramic filter candles, . . .)
Scrubber (Venturi scrubber, nozzle Wastewater and sludge
scrubber, packed tower, . . .) separated from the wastewater
SO2, SO3 Semidry and dry chemisorption Dry dust containing sulfites,
processes sulfates, and unreacted
sorbent
Limestone flue gas desulphurization Gypsum, wastewatera
(FGD)
Regenerative sorption processes SO2 gas (concentrated)b
(active coke, sodium sulfite, organic
solvents)
Absorption in basic solutions (NaOH, Sodium sulfate, ammonium
aqueous ammonia) sulfate, wastewatera
H2S and/or CS2 Regenerative sorption processes Elementary sulfur and/or CS2
(activated carbon, organic solvents) (concentrated)
Absorption (H2O2, NaOH) Sulfuric acid or sodium
sulfate
HCl, HF Semidry and dry chemisorption Dry dust containing chlorides,
processes fluorides, and unreacted
sorbent
Scrubber Wastewaterc
NOx Selective catalytic reduction (SCR) N2 and H2O in the off-gas
Selective non-catalytic reduction N2 and H2O in the off-gas
(SNCR)
NH3 Absorption Aqueous ammonia solution
CxHy or CxHyOz Condensation Liquid hydrocarbons
(volatile organic Post-combustion (thermal post- CO2 and H2O in the off-gas
compounds) combustion, catalytic post-
combustion)
Adsorption processes (activated Hydrocarbons (concentrated)
carbon, . . .)
Absorption processes (poly(ethylene Hydrocarbons (concentrated)
glycol) dimethyl ether, . . .)
Chlorinated Adsorption processes without Contaminated sorbent
hydrocarbons regeneration
Piniost-combustion under certain CO2, H2O, and HCl in the
conditions (temperature, residence off-gas
time)
a
Can be operated without wastewater under certain conditions
b
Can be used for production of sulfuric acid, elementary sulfur, or liquid SO2
c
Under certain circumstances hydrochloric acid can be produced
dry de-dusting and gas cleaning processes where an adsorbent or a reactant is added to
the off-gas which allows for a simultaneous separation of dust and gaseous pollutants
in the subsequent de-dusting system. In this case the resulting residue is a mixture of
the original dust, the adsorbent, or the reaction products and some unused reactant.
In the case of a wet de-dusting process the insoluble fraction of the dust becomes
suspended in the scrubber water and water-soluble components are dissolved. The
suspended solids are usually separated from the scrubber water by sedimentation or
filtration. The water content of the resulting sludge or filter cake depends on the
characteristics of the solids, especially the particle size distribution, and on the
separation process itself. Most of the scrubber water is reused in the scrubber.
However, some discharge of scrubber water is usually required in order to control
the concentration of dissolved ions (chlorides, sodium, potassium, . . .). Treatment of
this wastewater before discharge usually generates additional solid residues.
Desulfurization
The residues from separation of sulfur dioxide and sulfur trioxide from off-gas
can vary substantially depending on the type of desulfurization process applied
(Table 1). In the selection of a desulfurization process the off-gas parameters are
important, especially when a sellable product shall be produced. Semidry and dry
chemisorption processes produce a residue which is a mixture of sulfites, sulfates,
and unreacted sorbent. In contrast, aqueous sorption processes usually deliver sulfate
because sulfite can be oxidized more easily in the liquid phase. The resulting
products depend on the base added to the scrubber water. When lime-based sorbets
are used (limestone FGD) gypsum is precipitated. In the Walther process ammonia is
added to the scrubber water. The ammonium sulfate is recovered by evaporation of
the water. In the case of sodium hydroxide, wastewater rich in sodium sulfate is
discharged. In regenerative sorption processes, for example the Wellman-Lord
process (Neumann 1991) or the active coke process (Richter 1991) concentrated
sulfur dioxide gas is produced in the regeneration step. This can be processed further
to elemental sulfur (Claus process) and sulfuric acid or it is compressed to liquid
sulfur dioxide (Elsner et al. 2003).
Hydrogen sulfide and carbon disulfide can be separated from gas streams by adsorp-
tion on activated carbon or by absorption. In the regeneration step concentrated carbon
disulfide can be produced. Regenerated hydrogen sulfide from adsorption is usually
converted to elemental sulfur, while in absorption processes using hydrogen peroxide or
sodium hydroxide sulfuric acid or sodium sulfate is produced (Schultes 1996).
Separation of Hydrogen Chloride and Hydrogen Fluoride

In scrubbers, hydrogen chloride and hydrogen fluoride can be separated using water
as sorbent. Some of the scrubber water has to be discharged after neutralization. To
avoid high loads of salts in the discharged water the fluoride concentration can be
limited by precipitation of calcium fluoride using calcium hydroxide. Precipitation
of chlorides is not feasible on a technical scale. In the case of high concentrations of
hydrogen chloride, the production of a technical grade hydrochloric acid can be
considered (Joint Research Centre 2016a).
Reduction of Nitrogen Oxide Emissions

Nitrogen oxides are usually removed from off-gas by selective catalytic reduction
(SCR) or selective non-catalytic reduction (SNCR). In these processes the nitrogen
oxides react with ammonia or urea to form nitrogen and water vapor. The reaction
products are released to the atmosphere together with the off-gas.
Reduction of Ammonia Emissions

Ammonia can be removed from off-gas by absorption in water or acids. When no
other pollutants are contained in the gas and deionized water is used as absorbent,
aqueous ammonia can be produced.
Reduction of the Emissions of Volatile Organic Compounds

The most common method to reduce the emission of volatile organic compounds
(VOCs) is the oxidation of the components to carbon dioxide and water vapor. Both
reaction products are released to the atmosphere together with the off-gas. Various
designs for such a post-combustion process have been realized.
When valuable VOCs are present in a gas stream at higher concentration, conden-
sation of these VOCs at low temperature can be a feasible process. In this case the
residue from the gas cleaning process is a liquid mixture of organic components.
Another process for recovery of VOCs is adsorption on activated carbon. Alter-
natively, VOCs can be absorbed by an organic fluid having a low vapor pressure. In
the regeneration step concentrated hydrocarbons can be recovered.
Residues from Air Pollution Control in Major Industry Sectors
Cement Industry
APC in cement production is usually performed by de-dusting with ESPs or fabric
filters. The amount of dust separated from the off-gas of a cement kiln (cement kiln
dust, CKD) depends on the mode of operation of the plant: compound operation or
direct operation. In compound operation the amount of filter dust is in the range of
50–150 kg/t clinker produced, while in direct operation it is 80–200 kg/t clinker
(Schorcht et al. 2013). The dust is characterized by a composition similar to the
cement clinker with increased fractions of carbonate, chloride, and sulfate.
In the kiln system an internal circulation between the kiln and the preheater acts as
an enrichment cycle for volatile compounds. An increased input of chlorine, sulfur,
and alkalis with the raw materials or fuels leads to a high circulation of these
components. This enforces the use of a gas bypass at the kiln inlet. By discharging
part of the process gas, chlorine, sulfur and alkalis are removed from the cycle.
Typical bypass rates are up to 15% for chlorine bypass and up to 70% for a sulfur
bypass. De-dusting of the bypass gas produces the bypass dust which is character-
ized by an increased content of alkali chlorides or sulfates.
Iron and Steel Industry

For the production of steel from iron ore in an integrated steel mill several emission-
intensive process steps are required.
In a first step sinter is produced from fine-grained iron ore in the sinter plant.
APC in these plants is usually performed by de-dusting with ESPs or fabric filters.
The amount of dust separated is in the range of 0.2–3.6 kg/t sinter (Remus et al.
2013). In some sinter plants additionally a dry off-gas desulfurization process is
applied for gas cleaning.
In the blast furnace (BF) pig iron (hot metal) is produced from sinter, iron ore
pellets, and coke. The top-gas from the BF is usually de-dusted in two steps. In the
first stage, a dust-catcher or cyclone, the coarse dust is separated (BF dust) at a rate of
3.4–18 kg/t hot metal (Remus et al. 2013). In the second stage for the separation of
the fine dust a scrubber is usually applied. Most of the scrubber water is recirculated
after sedimentation of the particles which are discharged as sludge. The amount of
BF sludge is in the range of 2.0–22 kg/t hot metal (Remus et al. 2013). Some water
has to be discharged from the scrubber system to limit the concentration of dissolved
ions (chloride, . . .). The amount of wastewater is in the range of 0.1–13.7 m3/t hot
metal. In some BFs, especially in China, second-stage de-dusting is performed by a
fabric filter or an ESP. In this case the residue is a fine-grained BF dust. The cleaned
BF gas is utilized as a fuel. During tapping of the hot metal a considerable amount of
dust is produced in the cast house. In most BFs the cast house ventilation air is
de-dusted by an ESP or a fabric filter. The separated amount of cast house dust is in
the range of 0.6–5.1 kg/t hot metal (Remus et al. 2013).
In a further process step, the basic oxygen furnace (BOF), the hot metal is
converted into steel. The BOF off-gas can be de-dusted in a wet process (scrubber)
or a dry process (ESP). Subsequently, the clean BOF gas is used as a fuel. The
amount of solid residue remaining from de-dusting is 0.75–24 kg/t liquid steel
(Remus et al. 2013). In the case of a wet de-dusting system the amount of wastewater
is up to 6 m3/t liquid steel (Remus et al. 2013).
In the coke oven plant coal is converted to coke which is required in the BF
process. The off-gas from the coke ovens (coke oven gas, COG) is first cooled. In
this step high-boiling hydrocarbons are condensed and discharged as tar (26–48 kg/t
coke (Remus et al. 2013)). In a series of different downstream absorbers hydrogen
sulfide, ammonia, and light hydrocarbons are separated from the coke oven gas. The
light oil is recovered in the regeneration of the absorbent (9.1–14 kg/t coke (Remus
et al. 2013)). From the separated hydrogen sulfide and ammonia various products
can be produced (sulfuric acid, elemental sulfur, anhydrous ammonia, ammonium
sulfate) depending on the applied treatment processes. Finally, the clean COG is
used as a fuel.
Steel can be produced in a single step using iron scrap in an electric arc furnace
(EAF). The off-gas from EAF steelmaking is usually de-dusted in a fabric filter. The
amount of EAF dust is in the range of 10–30 kg/t of liquid steel (Remus et al. 2013).
Combustion and Incineration Plants

In the EU15 coal-fired power plants generated 48 million tons of combustion
residues in 2010. Most of these residues resulted from flue gas cleaning: 65% was
fly ash separated in de-dusting systems and 21% was gypsum from flue gas desul-
furization (Joint Research Centre 2016b).
The ash content of heavy fuel oil is usually well below 0.2% while the sulfur content
is between 0.5 and 2.2% (Joint Research Centre 2016b). Thus, the overwhelming share
of combustion residues in oil combustion results from off-gas desulfurization.
In biomass combustion plants various types of biomass (peat, wood, straw, . . .)
are used as fuel. The amount of fly ash separated in the de-dusting system depends
on the ash content of the used fuel and the type of combustion system. In grate-fired
combustion the fraction of fly ash is typically 30% of the total ash (Narodolawsky
and Obernberger 1996), while in fluidized-bed combustion this fraction is higher
than 80% (Joint Research Centre 2016b).
Due to the potentially high emission levels of waste incineration plants waste gas
cleaning is extensive in these plants. Thus various residues are generated depending
on the type of waste gas cleaning system. Typical amounts of APC residues in
municipal solid waste incinerators (MSWI) are in the case of a wet gas cleaning
system 20–40 kg boiler dust and 15–40 kg fly ash per ton of waste. In semidry and
dry gas cleaning systems the amount of fly ash is somewhat higher (20–50 kg/t
waste) (Joint Research Centre 2016a).
Oil Refineries
In oil refineries the main residue from APC processes is sulfur components from the
regeneration of absorptive desulfurization processes. These components are usually
converted into elemental sulfur in a Claus process. The sulfur recovery in modern
refineries is higher than 99%. Thus, the amount of residue depends mainly on the
sulfur input with the crude oil (Barthe et al. 2015).
Enrichment of Volatile Elements in the Off-Gas
In the off-gas from processes operated at high temperatures like combustion pro-
cesses or melting processes volatile elements are enriched. This leads to an enrich-
ment of these elements in the residues from off-gas cleaning. When the residues from
APC are recycled back into the process where they have been generated the volatile
components are usually cycled up in the process (Table 2).
The volatility of elements depends on the temperature in the process but also on the
presence or absence of other components like oxygen and chlorine. Important volatile
components with respect to up-cycling in APC systems are alkali chlorides (potassium
chloride, sodium chloride), some heavy metals (lead, zinc, cadmium, . . .), and sulfur
components.
Components volatilized in a process at high temperature usually recondense on dust
particles when the temperature of the off-gas decreases. As the specific surface area of
particles depends on the particle size also the concentration of the recondensed material
usually varies with the particle size. This dependence can be described approximately
by the relation c ~ 1/dN (Linak and Wendt 1993). The exponent N results from the
mechanism of condensation or reaction of the components on the particles. When the
concentration of a component has been measured in different size fractions of a dust the
exponent can be obtained by linear regression.
Table 2 Important volatile elements and components in some industrial high-temperature

processes
Process plants Residue Main problems caused
KCl, NaCl Iron ore sinter plant ESP Separation efficiency of ESP
dust
Cement kiln By-pass Kiln operation problems
dust
Biomass combustion plants Fly ash Ash melting behavior
using fuels like wheat straw or
Miscanthus
Zn Steel mill (electric arc furnace) EAF Energy demand for Zn reduction
dust and volatilization
Integrated steel mill (basic BOF Energy demand for Zn reduction
oxygen furnace) dust and volatilization
Integrated steel mill (blast BF dust Operation problems of furnace
furnace)
Copper smelter Dust Operation problems of furnace
As, Cd, Biomass combustion plants Fly ash Concentration above limit
Pb, Zn, . . . concentration makes use as soil
conditioner impossible
S Iron ore sinter plant Dry Reemission of sulfur components
DeSOx
residue
For several processes significantly increased concentrations of volatile compo-

nents were found in the finest size fractions of the dusts. This effect is used in some
APC systems consisting of more than one separation stage. In the first de-dusting
stage, e.g., a cyclone, the coarse dust is separated, while in the second stage, for
example an ESP, the fine dust is separated. As a consequence, the concentration of
the volatilized and recondensed components is lower in the dust from the first
de-dusting stage. Two- or three-stage du-dusting is applied, e.g., in BFs, for steel-
making off-gas or for the off-gas from biomass combustion plants.
Alternatively, classification of the separated dust can be applied to split a sepa-
rated dust into two fractions: a fine fraction with increased concentration of the
volatile components and a coarse fraction with lower concentrations.
Ways of Utilization of Air Pollution Control Residues
Use as Products
General
Some APC processes are designed in a way that the remaining residue is a product
that can be sold. Some additional processing of the residue is often required to
achieve this goal.
Gypsum
In the limestone FGD process the final product is gypsum. The sulfur dioxide is
absorbed in the scrubber suspension which contains limestone and some dissolved
oxygen. The sum equation of the reaction is:
SO2 þ CaCO3 þ ½ O2 þ 2 H2 O ! CaSO4 :2 H2 O þ CO2
Small gypsum crystals are also contained in the suspension as crystallization

nuclei for the produced gypsum. Classification in a hydro-cyclone separates the
coarse crystals for discharge, while the small crystals remain in the recirculated
suspension. The coarse gypsum crystals are further dewatered and sold as granular
material or briquetted after agglomeration. The gypsum is used in the building
material industry, for example for wallboard production, as plaster or as set retarder
in Portland cement. It can also be used in agriculture for acid soil amelioration or in
mining applications (Poullikkas 2015).
Sulfur Dioxide, Elemental Sulfur, and Sulfuric Acid

In regenerative sorption processes for off-gas desulfurization, for example in the
Wellman-Lord process, the active coke process or the Solinox process, concen-
trated sulfur dioxide gas is produced in the regeneration of the sorbent
(Poullikkas 2015). The sulfur dioxide can be compressed and liquefied. Alterna-
tively, it can be converted into elementary sulfur in a Claus process (Elsner et al.
2003):
SO2 þ 2 H2 S ! 3=2 S2 þ 2H2 O
The required hydrogen sulfide is produced from part of the sulfur dioxide by
reduction with hydrogen. Another option is the production of sulfuric acid.
In regenerative adsorption processes for the adsorption of hydrogen sulfide the
concentrated hydrogen sulfide gas obtained in the regeneration step is also converted
in a Claus process to elementary sulfur. The required sulfur dioxide is produced by
oxidation of part of the hydrogen sulfide.
Hydrochloric Acid
When large amounts of hydrochloric acid are separated from an off-gas by absorp-
tion in an aqueous solution, for example in the APC system of a waste incineration
plant, technical grade hydrochloric acid can be produced (Menke et al. 2003).
When the hydrochloric acid concentration in the off-gas is not extremely high only
diluted acid can be produced in the absorption process. Thus, a rectification step is
required. Simple rectification is only possible starting at a hydrochloric acid
concentration from the absorption process above the azeotropic point (20.2%w/
w). By adding additives (calcium chloride, magnesium chloride, . . .) to the diluted
hydrochloric acid, the phase equilibrium can be shifted in a manner that the
azeotropic point occurs at lower concentrations or disappears totally (Schultes
1996).
Volatile Organic Compounds

Volatile organic compounds separated from the off-gas by condensation, by regen-
erative absorption, or by adsorption processes (Gupta and Verma 2002) can be used
in appropriate applications.
CKD as Binder
CKD can be used directly to some extent by blending it with the cement produced
(Schorcht et al. 2013). The partial replacement of cement in concrete by CKD has
been investigated in numerous studies. The strength of the cured concrete decreased
somewhat (Shoaib et al. 2000) or even slightly improved (Maslehuddin et al. 2008).
Another possibility for utilization of CKD is the addition to lime mortar (Siddique
2006). In soil stabilization CKD can be used as an alternative to lime. In this case the
conventional compaction 2 days after the introduction is not necessary (Siddique 2006).
Fly Ash as Pozzolan

Fly ash from coal combustion plants is an artificial pozzolan (Ahmaruzzaman 2010).
A pozzolanic reaction is the volume-neutral chemical reaction of calcium hydroxide
and silicon dioxide forming calcium silicate hydrates:
x CaðOHÞ2 þ y SiO2 þ z H2 O ! x CaO • y SiO2 • ðx þ zÞ H2 O
Due to its pozzolanic properties fly ash contributes to structural and strength

formation of concrete. In DIN EN 206 (2014) fly ash is classified as additive type II
(pozzolanic additives). The fly ash may be used as a concrete additive if it meets the
requirements of DIN EN 450 (2012) which are met by most fly ashes from the
combustion of hard coal. Fly ash from the combustion of lignite fits to a much lesser
extent (Lutze and vom Berg 2004). According to DIN EN 197 (2011) the fly ash can
also be used directly in cement as a main component.
Fly Ash as Soil Ameliorant

In many countries the ashes from the combustion of chemically untreated biomass
are utilized as soil conditioner on agricultural land and forests. The recycling of
biomass ashes to the soil is proposed to help to close the nutrient cycles for the soil
where the biomass was grown. However, country-specific limit concentrations for
various heavy metals in the ash (e.g., arsenic, cadmium, chromium, copper, mercury,
nickel, lead, zinc) have to be observed (Lanzerstorfer 2014). Often the fly ash is
stabilized before it is spread onto the soil (Steenari and Lindqvist 1997).
Fly ash from the combustion of coal is also a useful ameliorant that may improve the
physical, chemical, and biological properties of problem soils and is a source of readily
available plant macro- and micronutrients (Jala and Goyal 2006; Basu et al. 2009).
Direct Recycling
Direct recycling of residues back into the process where the cleaned off-gas origi-
nated is possible in some cases. However, very often the residues contain elements or
components which are unwanted in the process. In such cases no recycling or only
partial recycling of the untreated residues is possible. The removal of the unwanted
elements or components before the recycling can be an alternative. For this treatment
process, e.g., leaching, thermal treatment or classification can be applied.
Volatile Organic Compounds

When volatile organic compounds, for example solvents, are separated from the
off-gas by condensation these VOCs are often reused in the same process.
Dust
When the enrichment of unwanted elements or components is small, dusts can often
be recycled, at least partially, back into the process from which they originate.
Another limitation for direct recycling can be the fine grain size of a dust. An
example for direct dust recycling is the use of the iron-rich ESP dust of iron ore
sinter plants as feed material of the sintering process (Remus et al. 2013). In cement
plants the composition of CKD is similar to cement. Thus, it can be recycled back to
the kiln (Schorcht et al. 2013). However, in both cases the content of alkali salts can
be a limiting factor. EAF dust can also be recycled back into the furnace. To avoid
increased reemission of dust it is injected into the liquid bath (Jensen and Wolf
1997). Also dust from dry de-dusting of BOFs can be recycled by being injected into
the furnace (Forsthuber and Enkner 1998).
Treatment of Residues for Recycling or Utilization
In many cases the dusts have to be treated before they can be recycled. Unwanted
components in dust can be removed by leaching (hydrometallurgical) processes and
by thermal (pyrometallurgical) processes.
Because of the fine grain size, the recycled dust often has to be agglomerated
before recycling to limit immediate re-entrainment of the recycled dust.
Agglomeration of Dust
Recycling of a dust back into a process can increase the rate of dust generation
substantially. Because of the small grain size, the particles are re-discharged easily
by the produced off-gas. In such cases agglomeration of the dust prior to recycling is
required. The two main processes used for agglomeration of dust are pelletizing and
press agglomeration (briquetting).
Pelletizing is a wet nonpressure agglomeration method which produces round
pellets. It requires the use of a binder to foster particle size enlargement. The fine-
grained material is fed onto a disc pelletizer or a drum pelletizer where the pellets are
grown by tumbling the fines against themselves in the presence of the binder. Once
the pellets have reached the desired size they exit the pelletizer.
In the case of press agglomeration, external forces are applied to the dry dust by
means of pressing tools. Many contacts are being formed between the particles. The
cavity area is reduced, brittle primary particles can break, and plastic particles are
deformed. In press agglomeration, binders may be added to increase the agglomerate

strength. Typical binders used are molasses, water glass, or bentonite.
EAF dust is often agglomerated before it is recycled to reduce reemission.
Carbonaceous material can be added to the mixture to compensate for the increased
energy demand of the recycled material (Bacinschi et al. 2012; Lopez and Lopez-
Delgado 2002; Wu et al. 2017). In a similar way the sludge from BOF gas wet
de-dusting can be agglomerated and recycled into the furnace (Su et al. 2004). Dust
from BOF dry de-dusting can be briquetted for recycling at a material temperature of
500–700 C because of its metallic iron content. During hot briquetting sintering
bridges occur between the particles (Pietsch 1994).
Recently, the agglomeration of BF sludge with starch binder for recycling has
been investigated (Drobíková et al. 2016).
Granulation of a dust can be used to increase the dust bulk density for transport or
landfill. Such granules, which are matured by intermediate storage, exhibit high
mechanical stability and abrasion resistance as well as improved dust behavior
(Salihoglu and Pinarli 2009).
Leaching
Leaching can be applied for the extraction of some species from a residue, aiming to
improve the quality of the residue for further utilization and/or to recover the species in
question. Leaching of residues which are hazardous waste aims to allow disposal on
nonhazardous waste landfill sites (Amutha Rani et al. 2008). Besides water, various
acidic and basic leaching agents have been investigated in different applications
depending on the solubility of the respective components. Leaching processes have
been investigated widely for example for EAF dust (Jha et al. 2001) and MSWI fly ash
(Quina et al. 2008). A reduction of the content of critical heavy metals in wood
combustion fly ash can also be achieved by leaching (Lanzerstorfer and Kröppl
2018). Leaching with water can be applied to recover potassium chloride from cement
kiln bypass dust (Sturm and Galichet 2012) or biomass combustion fly ash.
Thermal Treatment
Thermal treatment can be applied for the volatilization of some species from the dust
to improve the quality of the residue for further utilization and/or to recover the
volatilized components. Thermal treatment has been investigated for example for
MSWI fly ash (Quina et al. 2008; Nowak et al. 2010). The treatment is capable of
removing the more volatile heavy metals like cadmium and lead.
Thermal treatment can be used to obtain residues with improved leaching char-
acteristics as well as a treated material that is suitable for reuse. In a vitrification
process the residues are mixed with glass precursor materials and then combined at a
temperature of 1000–1500 C into a single-phase amorphous glassy product. In
melting processes similar temperatures are applied but without addition of glass
materials resulting in a multiple-phased product. In a sintering process the temper-
ature is around 900 C. Bonding of particles occurs and chemical phases in the
residues reconfigure (Sabbas et al. 2003). These techniques show the potential of
stabilizing hazardous waste and producing reusable materials.
Classification
Classification of the sludge obtained from the wet cleaning of BF off-gas has become
a common treatment procedure (Remus et al. 2013). Thereby, the sludge is separated
by hydro-cyclones into two size fractions. The coarse fraction is less contaminated
with zinc and therefore can be added to the feed material of the sinter plant. Residues
from dry de-dusting can be classified in a similar way using a shifter or air classifier.
Classification of the residue from dry BF off-gas de-dusting for zinc enrichment and
depletion has been suggested (Lanzerstorfer and Kröppl 2014). In a similar way air
classification could also be applied for steelmaking dust (Lanzerstorfer 2018).
Use of Residues in Another Process
Iron Ore Sinter Plant

In integrated steel mills the sintering process is applied to agglomerate the fine ore
before it can be processed in the BF. The sinter strand is also used to recycle the fine-
grained iron-bearing residues generated at various process steps in steel production.
Thus, a lot of the residues from off-gas de-dusting processes are also recycled via
this process (Hansmann et al. 2008). However, there are some limitations for the
inclusion of dusts in sintering. These are the alkali chloride content of the dust and
the content of VOCs, lead, and zinc. The limit for alkali chlorides arises from the
operating conditions for the ESP used for APC because high concentrations of alkali
chlorides increase the specific dust resistivity above the limit for reasonable ESP
separation efficiency. A high load of VOCs can cause the risk of fire in the ESP
because the specific combustion conditions in the sintering process cause the
volatilization of a large fraction of the VOCs in the process. The recondensed
VOCs stick to the dust particles. When the content of VOCs in the separated dust
is high the sparks occurring in the ESP can cause a fire.
The limit for lead and zinc does not arise from the sintering process itself but from
the quality requirements for the sinter produced. A high amount of lead and zinc fed
to the BF causes operational problems in BF operation and the sintering process is
not very effective in volatilization of zinc (Lanzerstorfer et al. 2015).
Cement Kiln
The correct proportions of calcium, silicon, aluminum, and iron in Portland cement
are specified within rather strict limits. To provide each of the main elements of the
cement also residues from APC, especially fly ash from coal combustion and some
steel mill dusts are used as part of the feed (Barthe et al. 2015; Koros 2003).
Pyrometallurgical Zn Recovery
Dusts from steelmaking with an increased zinc content are often processed for zinc
recovery. Several processes have been developed to achieve this goal but only the
Waelz kiln reached widespread application. It accounts for about 75% of the total
treated EAF dust globally (Lin et al. 2017). In these processes the zinc is volatilized
by reduction to metallic zinc. Crude zinc oxide is recovered from the process off-gas
which is a valuable raw material for zinc production. In the Waelz process the
remaining slag is sent to landfill, while in other processes (rotary hearth furnace,
the PRIMUS® process, and OXYCUP ® process) the iron-rich residue is use in the
iron production step (Antrekowitsch et al. 2015; Holtzer et al. 2015). As still no
optimal solution for recovery of zinc from ironmaking and steelmaking dusts is
available research in this area is continuing (Lin et al. 2017; Antrekowitsch et al.
2015).
Recovery of Alumina
The recovery of alumina from coal fly ash was pioneered by Grzymek in Poland. In
recent years several plants for alumina recovery from coal fly ash have been installed
in China (Yao et al. 2014). The feasibility of alumina recovery from fly ash mainly
depends on its alumina content. Usually fly ash with an alumina content of more than
30% can be considered viable for the recovery of alumina.
New Ways of Utilization
Production of Potassium Chloride for Fertilizer

Potassium can be enriched in several dusts: in sinter plant dust, in cement kiln bypass
dust, and in fly ash from biomass combustion. In recent years, increasing research
efforts in recovery of potassium chloride for fertilizer production are evident (Maeda
et al. 2017; Lanzerstorfer 2016; Peng et al. 2009; Zhan and Guo 2013; Yu et al.
2017). A first plant for production of potassium chloride from cement mill bypass
dust on an industrial scale was built in 2011 (Sturm and Galichet 2012).
In air classification tests with the dust from sinter plant de-dusting (Lanzerstorfer
2015a), bypass dust from a cement kiln (Lanzerstorfer 2016) and biomass combus-
tion fly ash (Lanzerstorfer 2011, 2015b), it has been demonstrated that a fine dust
fraction with a significantly higher potassium chloride concentration can be sepa-
rated from the bulk. Processing dust with a higher potassium chloride content should
improve the efficiency and economy of the winning process. In the case of sintering
dust and bypass dust the remaining coarse fraction depleted in potassium chloride
could be recycled in the respective process.
Glass-Ceramics
The production of glass-ceramic from various silicate-rich air pollution control
residues (waste incineration fly ash, coal fly ash, EAF dust, CKD, . . .) has been
investigated for a long time. Although several studies have shown promising results,
widespread industrial production of useful glass-ceramics including APC residues is
not yet achieved (Rawlings et al. 2006; Barbieri et al. 1999). For example, fly ashes
originating from APC at MSWIs can be mixed with different amounts of inert
materials such as glass cullet and feldspar waste to vitrifiable mixtures. The glasses
obtained by means of the vitrification process were chemically stable showing a low
leachability of contaminants. The material properties were comparable to those of
commercial soda-lime glasses (Andreola et al. 2008).
Ceramics
The use of EAF dust as raw material for ceramic building products has been
investigated. Use of up to 20% of EAF dust showed acceptable properties of the
produced material. In leaching tests with the material produced the heavy metal
concentrations were below the acceptable limits (Sikalidis and Mitrakas 2006;
Machado et al. 2011).
Production of Zeolites
Several studies have shown that coal combustion fly ash can be used to synthesize
zeolites (Querol et al. 2002). Zeolites are crystalline aluminum silicates, with group I
or II elements as counterions. As a consequence of the structural properties of
zeolites, they have a wide range of industrial applications mainly based on ion
exchange, gas adsorption, and water adsorption. Current research is into the pro-
cessing of the fly ash targets to improve zeolite yield and transformation efficiency
(Yao et al. 2015).
Landfill
General
Disposal of material ranks lowest in the waste hierarchy. However, safe disposal of
non-recoverable residues, especially hazardous material, is still an important part of
APC residue management.
Backfilling in Mines
Backfilling means the back stowing of mines for safety reasons. Mine cavities that
have resulted from the exploitation of natural resources by mining are filled with
appropriate industrial wastes. Backfilling has been approved by the European Court
as a form of recycling on condition that by means of a necessary measure natural
resources are being substituted by industrial wastes and resources are protected
(Marx et al. 2005). For environmental protection limiting values of harmful sub-
stances within waste and the leaching behavior have to be considered. However,
these limiting values are not valid for salt mines which completely enclose the
harmful substances, thus permanently closing them from the biosphere.
Hazardous APC residues can be dumped safely in underground salt caverns.
Thereby, different methods for backfilling are applied: hydraulic backfilling and big
bag backfilling. In hydraulic backfilling the fine-grained APC residues are usually
processed into a flowable backfilling mixture by adding a concentrated salt solution
as a transporting medium on the surface and remain in a reaction drum to reduce
exothermal effects and possibly existing gas production potential. After a residence
time of few hours the mixture is transported into the recoveries to be backfilled by
means of a piping system. The excess transporting solution drains the backfilling
material by means of a barrier system. It is collected in a basin at a deeper point of
the mine and subsequently transported back into the process on the surface (circu-
lation of the transporting solution). By means of hydraulic backfilling a
nearly complete backfilling (>90 Vol. %) of the mining sites is possible (Marx
et al. 2005).
In big bag backfilling the big bags are transported into the underground via the
shaft and big vehicles transport them into the backfilling chambers. Forklift trucks
install the big bags into the backfilling chambers in layers. Alternating storage with
covering salts is applied to reduce the pores.
Solidification
Solidification is a pre-landfill waste treatment that aims to make hazardous APC

safe for disposal. This process involves mixing APC into a binder system. A wide
range of binders (cementitious binders, lime, bitumen) have been used for
solidification. The aim is to incorporate the APC into the binder system and
produce a monolithic solid with structural integrity and long-term stability. Thus,
solidification should also inhibit leaching (Amutha Rani et al. 2008).
APC Residues from Waste Incineration Plants

MSWI fly ash can be stabilized by mixing with cement to reduce leaching of heavy
metals (Shi and Kann 2009). By leaching of the fly ash with water for the removal of
soluble salts the amount of fly ash that may be incorporated into the cementitious
matrices is significantly increased (Mangialardi et al. 1999).
By-Product from Semidry and Dry Sorption Processes for Acid Gases
When calcium-based sorbets are used the by-product from semidry and dry chem-
isorption processes typically consists of calcium sulfate, calcium sulfite, and calcium
chloride also including carbonates and unreacted lime. The content of fly ash varies
between 1 and 80% (by mass) depending on the degree of pre-de-dusting. Normally,
the by-product is disposed of. However, industrial utilization may be possible in the
future (Poullikkas 2015).
In some plants mixed sorbents—hydrated lime and activated carbon—are used
for integrated separation of acid gases and toxic organic compounds, for example
PCDD/F. In such plants the by-product also contains these toxic components.
EAF Dust
EAF dust can be stabilized before dumping to minimize leaching of heavy metals.
Stabilization with lime and/or Portland cement has been investigated (Salihoglu and
Pinarli 2009). It was found that the best results were achieved with a mixture of lime
and Portland cement of 1:1, since the pH of the suspension was shifted to the slightly
basic range. With this additive mixture, total mixtures with 30% EAF dust could be
stabilized.
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Part VI
Environmental Analysis
Tailor-Made Molecular Traps for the
Treatment of Environmental Samples 36
Rüstem Keçili, Özlem Biçen Ünlüer, and
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 930
MIP-Based Molecular Traps for Solid Phase Extraction of Pharmaceuticals from
Environmental Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 931
Ion Imprinted Traps for Solid Phase Extraction of Metals from Environmental Samples . . . . 936
MIP-Based Molecular Traps for Solid Phase Extraction of Dye Compounds from
Environmental Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 939
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 942
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 945
Abstract
Environmental pollution is one of the serious global problems today. Many
hazardous compounds in environmental samples such as heavy metals, drugs,
and dye compounds phenolics, herbicides and pesticides, etc. are main sources of
environmental pollution, and they may cause serious diseases in humans, ani-
mals, and plants. Thus, analysis and efficient removal of these undesired com-
pounds from environmental samples such as wastewater and soil is a crucial task.
Traditional materials such as activated carbon are commonly used for the treat-
ment of environmental samples. However, it has some disadvantages such as
regeneration problems and high cost. These challenges can be overcome by using
R. Keçili (*)
Yunus Emre Vocational School of Health Services, Department of Medical Services and
Techniques, Anadolu University, Eskişehir, Turkey
e-mail: rkecili@anadolu.edu.tr
Ö. Biçen Ünlüer
Faculty of Science, Department of Chemistry, Anadolu University, Eskişehir, Turkey
C. M. Hussain
NJ, USA

https://doi.org/10.1007/978-3-319-73645-7_24
930 R. Keçili et al.
tailor-made traps called molecularly imprinted polymers (MIPs). MIPs are highly
cross-linked resins having selective binding groups and cavities toward the target
compound.
In this chapter, we provide the recent progresses of new MIP materials for the
removal of pollutants such as pharmaceuticals, metal ions, and dye compounds
from environmental samples.
Keywords
Molecularly imprinted polymers (MIPs) · Molecular traps · Extraction ·
Treatment · Environmental samples · Wastewater
Introduction
Molecularly imprinted polymers (MIPs) are engineered molecular traps that possess
specific recognition sites with high affinity and selectivity toward the target compound
(Fig. 1). Therefore, MIPs can be used in many applications where selective binding
phenomena is crucial, such as solid phase extraction, biosensors, and catalysis (Sellergren
2001; Kryscioa and Peppas 2012; Cheong et al. 2013; Vasapollo et al. 2011; Chen et al.
2012a, b; Guerreiro et al. 2011; Lai and Feng 2003; Wang and Wei 2017; Keçili et al.
2011, 2012; Kupai et al. 2017; Erdem et al. 2010; Cui et al. 2015; Prasad et al. 2010).
Environmental pollution is one of the significant international concerns. Various
chemicals in water such as pharmaceuticals, heavy metals, dye compounds, etc.
exhibit harmful effects on human body, animals, and plants. Thus, selective recog-
nition and extraction of these compounds from environmental samples are crucial.
Fig. 1 The principle of

molecular imprinting Y
(Reproduced with
permission from Lofgreen
and Ozin 2014) Functional monomer
imprint imprint
Y
Polymerization with Y
cross-linker
Removal of target
imprint
or
target
36 Tailor-Made Molecular Traps for the Treatment of Environmental Samples 931
Traditional approaches such as gas chromatography (GC) and high-performance

liquid chromatography (HPLC) were used for the trace analysis of these undesired
chemicals in environmental matrices (Bagheri et al. 2004; Bonwick et al. 1995;
Hladik et al. 2008). But these techniques are time-consuming and expensive.
These drawbacks of traditional techniques can be overcome by preparation of
MIP-based micro- and nanomaterials which exhibit high selectivity and affinity
toward target compound. In this chapter, recent developments and environmental
applications of MIP-based selective materials in micro- and nanoscale were provided.
MIP-Based Molecular Traps for Solid Phase Extraction

of Pharmaceuticals from Environmental Samples
Solid-phase extraction (SPE) is one of the powerful tools for sample preparation in
analytical chemistry. The researchers experimentally applied this technique in the
late of 1940s (Liska 2000), and the developments which lead to use of SPE in the
current analytical applications were started in the early 1970s. It is now widely used
in many different areas in analytical chemistry such as preconcentration, purification,
fractionation, etc.
Various traditional SPE resins such as silica-based (Cazes 2009; Spivakov et al.
2006), carbon-based (Pyrzynska 2007; Rodríguez et al. 2015), and clay-based
(Valdes et al. 2006) materials have been used in different SPE applications. Most
of these SPE resins are now commercially available as SPE tube and pipet tip format
such as Oasis-HLB (manufactured by Waters) and Omix (manufactured by Agilent),
MonoTips (manufactured by GL Sciences).
Even though SPE is a popular and widely used analytical tool for sample cleanup
and preconcentration of target compounds from complex samples, the traditional
materials used for SPE applications show lower selectivity toward desired analytes
which leads to binding of interfering compounds in the sample matrix. Molecularly
imprinted polymers (MIPs) as promising SPE resins which display higher selectivity
and affinity toward target compound can overcome these disadvantages.
MIPs are selective for a target compound or group of compounds and allow
preconcentration of these target compound(s) in the presence of other interfering
compounds in the sample matrix. Another superiority of the MIPs compared to
conventional SPE resins is their stability under extreme conditions. Compared to
various SPE materials, MIPs are stable under harsher chemical conditions such as
high temperature and higher and lower pH values.
MIPs are widely used as SPE materials in many different samples such as
environmental samples, biological samples, and food samples. The interaction and
binding between the target compound in the sample matrix and the MIP can be
driven by various chemical interactions such as polar, covalent, non-covalent, and
hydrophobic interactions.
A typical SPE protocol using MIP resins composed of four different steps as
briefly explained in the following:
1. Conditioning step: The MIP-based SPE material in the column needs to be

washed with an appropriate solvent to remove undesired impurities, and then it
is conditioned with the loading solvent. The specific binding sites of the polymer
should be activated by performing conditioning step to maximize the interactions
with the target compound. It should be noted that the polymer should not be dried
during conditioning step as this may lead to recovery of the target compound in
lower values.
2. Sample loading step: Sample loading is carried out after the conditioning step. In
this step, the sample is loaded onto the SPE column filled with MIP to interact
target compound in the matrix with the polymer. The matrix medium affects the
binding properties of the target compound to the MIP. The binding (imprinted)
sites of the MIP usually interact with the target compound by H-bonding, ionic
interactions, or π-π interactions. Thus, solvents that have low polarity are used
in the sample loading step to obtain a selective binding of the target compound to
the polymer.
3. Washing step: After sample loading, the washing step is applied. When water is
used as the medium for target compound, other undesired compounds in the
sample matrix are non-specifically bound to the MIP by hydrophobic interactions.
Therefore, a washing step using an organic solvent should be performed to disrupt
undesired non-specific hydrophobic bonds. It also is crucial to dry the polymer in
the column between the loading and washing step in order to avoid miscibility
problems when changing from aqueous medium to organic medium. On the other
hand, the binding ability of the target compound to the MIP may be effected
during the washing step. This step is more crucial in SPE using MIPs than in SPE
using traditional materials. The main aim of the washing step is to increase the
specific interactions between the target compound in the sample and the prepared
MIP in SPE cartridge and to elute other undesired interfering compounds in the
sample. In general, an organic solvent that has low polarity such as DCM and
CHCl3 is used as washing solvent.
4. Elution step: The last step of a typical SPE is elution step which is sometimes
composed of one or more steps, where the specific interactions between target
compound and the MIP are disrupted. MeCN or MeOH is commonly used as the
elution solvent in MIP-based SPE. During the elution step, small volumes of
elution solvent are used to get high enrichment factors. In some cases, the specific
interactions between target compound and the MIP are very strong. Therefore, a
weak acid such as acetic acid or a weak base such as trimethylamine should be
used to get high recovery values.
The group of Sellergren reported the first use of MIPs in SPE applications
(Sellergren 1994). In this study reported in 1994, MIP for selective binding and
extraction of pentamidine which is a pharmaceutical compound used for the AIDS
patients was prepared and successfully applied for SPE of target compound pent-
amidine. After this work, a lot of effort was put into the design and preparation of
novel MIPs toward different compounds for selective SPE applications in different
areas (Caro et al. 2003; Chapuis et al. 2004; Lai et al. 2004; Brüggemann et al. 2004;
Puoci et al. 2012; Xin et al. 2013; Li et al. 2014; He et al. 2016a; Han et al. 2015;
Morais et al. 2017; Vasconcelos and Fernandes 2017; Ansari and Karimi 2017).
Terzopoulou and co-workers developed molecularly imprinted fiber-based mate-
rials for selective extraction of abacavir which is an antiviral compound
(Terzopoulou et al. 2016). In this work, free radical polymerization of the functional
monomer acrylic acid (AA) and ethylene glycol dimethacrylate (EGDMA) was
carried out in the presence of the template abacavir. After removal of the template
from polymeric structure by using soxhlet extraction with MeOH and EtOH, the
obtained abacavir imprinted fibers were used for the extraction of abacavir in
biological and environmental samples. The results indicated that the prepared
molecularly imprinted fibers displayed high affinity and selectivity toward the target
compound abacavir and the maximum binding capacity of the imprinted fibers was
found to be as 149 mgg1 at pH 8.0.
Magnetic nanoparticles have drawn significant interest in separation science due
to their advantages such as low cost, low toxicity, high chemical stability, and
excellent recovery capability from complex sample matrices. Combination of mag-
netic nanoparticles with MIPs increases selectivity and affinity toward target com-
pound and provides a new approach for separation applications. In a study published
by Chen et al. (2015), magnetic MIPs for the selective SPE of antibacterial sulfadi-
azine drug were prepared. The functional monomer acrylamide (AAm) and the
cross-linker EGDMA were used for the preparation of the magnetic MIPs toward
sulfadiazine. The sulfadiazine binding to the prepared magnetic MIPs was carried
out in the presence of other competing compounds such as sulfacetamide,
sulfamethazine, and sulfamethoxazole. The results obtained from these experiments
confirmed that molecularly imprinted magnetic beads showed high selectivity
toward the target drug sulfadiazine. The highest binding of sulfadiazine to the MIP
beads was achieved within 7 min. The maximum binding capacity of the magnetic
MIPs was 775 μgg1.
In another reported study, MIP beads for selective SPE of enrofloxacin which is
an antimicrobial veterinary drug were prepared (Benito-Peña et al. 2015). For this
purpose, methacrylic acid (MAA) and 2-hydroxyethyl metharcrylate (HEMA) were
used as the functional monomer and hydrophilic comonomer, respectively (Fig. 2).
The prepared molecularly imprinted spherical particles enrofloxacin were applied for
the selective extraction of enrofloxacin. The outcomes from the SPE experiments
showed that enrofloxacin-selective MIPs exhibited high affinity and selectivity
toward the target compound with a Ka value of 7558 M1.
Kyzas and his colleagues prepared MIPs for selective extraction of metformin
from wastewater (Kyzas et al. 2015). In their study, functional monomer AA and
cross-linker EGDMA were used for the preparation of metformin selective-MIPs.
The extraction performance of the prepared MIPs toward the target drug metformin
was investigated under different conditions including medium pH, interaction time,
and initial drug concentration. Figure 3 shows the schematic depiction of the
prepared MIPs and extraction procedure. The results showed that the prepared
MIPs exhibited excellent affinity and selectivity toward metformin with a binding
capacity of 80 mgg1.
O
OH
O O−
F
O O
− N N
O H
N+
O−
O
Fig. 2 Molecularly imprinted beads toward enrofloxacin (Reproduced with permission from
Benito-Peña et al. 2015)
Cavity Low affinity site
Medium affinity site Drug
Imprinting
cavity
MIPs after extraction MIPs after sorption
Dispersion of MIP Nanoparticles

To aqueous solution
MIPs
Elution with Centrifugation
Sorption of Separation of Removal of Organic Upper phase
Analytes phases aqueous Solvent
Stirring Centrifugation phase Ultra

sonication Introduction
to LC-MS
Fig. 3 Schematic depiction of the prepared MIPs and extraction procedure (Reproduced with
permission from Kyzas et al. 2015)
Another interesting work was reported by Tan et al. (2013a) on the pre-
paration of MIP nanoparticles for the removal of ofloxacin from aqueous
solutions. For this purpose, surface of the mesoporous carbon nanoparticles
was covalently grafted with MIP nanoparticles. MIP nanoparticles were pre-
pared by using MAA and TRIM as functional monomer and cross-linker, respec-
tively. The prepared MIP-based nanocomposite displayed high affinity and
selectivity toward ofloxacin in the presence of other fluoroquinolone anti-
biotics such as balofloxacin, sarafloxacin, norfloxacin, gatifloxacin, and
enrofloxacin. The maximum binding capacity of the prepared nanocomposite
was 40.98 mgg1.
In another research reported by Olcer et al. (2017), a MIP-based SPE adsorbent

was prepared for the extraction of ibuprofen (IBU) from drinking and tap water
samples. For this purpose, selective MIPs toward ibuprofen were prepared by
polymerization of the functional monomer MAA and the cross-linker TRIM in the
presence of target drug ibuprofen. The schematic representation of the preparation of
MIP toward IBU is shown in Fig. 4. The prepared MIPs exhibited high affinity and
selectivity toward IBU in the presence of ketoprofen and naproxen. The developed
method was also validated, and the obtained recoveries were 97.2% and 97.7% for
drinking and tap water, respectively.
Li et al. reported the use of molecularly imprinted magnetic Fe3O4@SiO2 parti-
cles for the recognition and extraction of tadalafil from pharmaceutical samples
(Li et al. 2011). Different functional monomers AA, MAA, and 2-(trifluoromethyl)
acrylic acid (TFMAA) were tested for the preparation of three different MIPs and the
binding energy results indicated that TFMAA exhibited strongest interaction with
the target compound tadalafil. Figure 5 shows the SEM and TEM images of the
Fig. 4 TEM (small image) and SEM images of (a) Fe3O4 particles, (b) Fe3O4/SiO2 particles, and
(c) Fe3O4/SiO2 particles coated with MIP film toward tadalafil (Reproduced with permission from
Li et al. 2011)
160
Extraction amounts (mmol g-1)
N
140 O
N
O
N
z O
O O
120
N
z
O O
O
S
100
NH
NH
O
80
NH
O
N
O
60
N
N
40
N
20
0
4
)
T-MIPs
l L -1
T-NIPs
S-MIPs
S-NIPs 2
mo
V-MIPs
V-NIPs
(m
Fig. 5 Selectivity of magnetic MIP nanoparticles toward tadalafil (Reproduced with permission
from Li et al. 2011)
synthesized Fe3O4 nanoparticles, Fe3O4@SiO2 nanoparticles and Fe3O4@SiO2

nanoparticles coated with MIP film toward tadalafil.
The prepared molecularly imprinted magnetic Fe3O4@SiO2 nanoparticles were
successfully applied for the selective extraction of tadalafil (T) in the presence of
sildenafil (S) and vardenafil (V). The prepared magnetic Fe3O4@SiO2 nanoparticles
coated with MIP film displayed high selectivity toward target compound tadalafil
with an extraction capacity of 140 μmolg1 (Fig. 5). The control non-imprinted
nanoparticles exhibited lower binding behavior toward all compounds.
The group of Xu reported the preparation of molecularly imprinted magnetic
cellulose microbeads for selective extraction of artesunate (Huang et al. 2016). For
this purpose, MIP shell was prepared on the surface of magnetic Fe3O4-cellulose
composite beads by using surface imprinting approach. The obtained results showed
that the prepared molecularly imprinted magnetic cellulose microbeads exhibited
high affinity toward artesunate with a maximum binding capacity of 220 mgg1. The
highest artesunate extraction was achieved in 10 h.
Ion Imprinted Traps for Solid Phase Extraction of Metals from

Environmental Samples
Ion imprinted polymers (IIPs) as selective traps toward target ions were first intro-
duced by Nishide and co-workers in 1976 (Nishide et al. 1976). The process for the
preparation IIPs involves the following steps:
• Complex formation between the functional monomer and target ion

• Polymerization in the presence of cross-linker
• Removal of the target ion from polymeric structure
The obtained IIP has binding cavities that exhibit high affinity and selectivity
toward target ion. In recent years, various IIPs were used for the extraction of metals
from environmental matrices. For example, Zhang and his colleagues have prepared
IIP-based magnetic nanocomposites for Pb2+ extraction from environmental samples
(Zhang et al. 2011). 3-(2-Aminoethylamino)propyltrimethoxysilane (AAPTS) as the
functional monomer, tetraethylorthosilicate (TEOS) as the cross-linker, and template
ion Pb2+ were used for the preparation of nanocomposites toward Pb2+ ions. Figure 6
shows the schematic depiction of the prepared ion imprinted magnetic nano-
composites for Pb2+ ions. Different factors which effect the selective extraction of
target ion such as pH and sample volume were studied. The results obtained from
SPE studies for Pb2+ in the presence of other potential interfering ions such as Zn2+,
Cd2+, and Hg2+ in environmental samples showed that the prepared MIP-based
magnetic nanocomposites display high selectivity toward Pb2+ ions. The binding
capacity of the nanocomposites for Pb2+ ions was determined as 19.61 mgg1.
A clay-IIP nanocomposite for selective extraction of Fe3+ ions from aqueous
solutions was prepared by Karabörk et al. (2008). In their study, the intercalation
of quartamine cations was performed by an ion exchange process between the
smectite host and quartamine. Fe3+ ions were complexed with N-methacryloylamido
antipyrine (MAAP) as the functional monomer. The results obtained from SPE
TEOS AAPTS, Pb(II) Adsorption
NH3H2O Desorption
TEOS, NH3H2O
Fe3O4 Fe3O4@SiO2 Fe3O4@SiO2@IIP
HN NH2 N NH2
Desorption H
Pb2+
H
H2N NH Adsorption H2N N
Template Imprinted sites
Fig. 6 Schematic depiction of ion imprinted magnetic nanocomposites for Pb2+ (Reproduced with
permission from Zhang et al. 2011)
experiments showed that the prepared clay-MIP nanocomposite showed high selec-
tivity toward Fe3+ ions. The binding capacity of the clay-MIP nanocomposite was
found to be 78.5 mgg1.
In another interesting study, Nd3+ imprinted polymers were prepared by Dolak et al.
(2015). N-methacryloylamido folic acid (MAFol) and EGDMA were used as the func-
tional monomer and cross-linker, respectively. The effects of various factors such as
medium pH, initial metal concentration, and interaction time on Nd3+ binding to the
prepared ion imprinted polymers were investigated. The equilibrium time for Nd3+ binding
was obtained in 30 min. The prepared ion imprinted polymers showed high selectivity
toward Nd3+ ions in the presence of other interfering ions such as Ce3+, La3+, and Eu3+,
and maximum capacity of the prepared ion imprinted polymers was 14.6 mgg1.
Li and co-workers prepared IIP-based carbon nanotube/chitosan composite for
the selective extraction of Gd3+ from aqueous solutions (Li et al. 2015). In their
study, magnetic silica nanoparticles (SiO2@Fe3O4) and Gd3+ imprinted carbon
nanotube-chitosan composite were dispersed in aqueous solution of rare earth
metals. The schematic depiction of the extraction process using magnetized-Gd3+
imprinted nanocomposite is given in Fig. 7. The obtained results showed that
selective extraction of Gd3+ ions in the presence of other ions such as Ce3+ and
La3+ were successfully achieved. The binding capacity IIP-based carbon nanotube-
chitosan composite toward Gd3+ ions was found to be 88 mgg1.
Another IIP toward Lu3+ was prepared by Lai et al. (2012). For this purpose,
4-vinylpyridine-acetylacetone- Lu3+ and EGDMA were used as the complex func-
tional monomer and cross-linker, respectively. The obtained results showed that the
highest Lu3+ binding to the prepared IIP was achieved at pH 5.5 within 30 min and
the maximum binding capacity was found as 64.2 mgg1.
A novel core-shell IIPs were prepared by Liu and colleagues for the selective
removal of Co2+ ions from aqueous solutions (Liu et al. 2015a). For this purpose,
3-aminopropyltriethoxysilane (APTS) and acryloyl chloride (AC) were used for the
modification of silica particles, and photopolymerization was then carried out using
acrylamide (AM) as the functional monomer in the presence of template ion Co2+
(SiO2@Fe3O4)
(Carbon
Gd3+-imprinted
nanotube) : Gd3+
site
: Ce3+
: La3+
Fig. 7 Schematic depiction of the extraction process using Gd3+ imprinted magnetic nano-
composite (Reproduced with permission from Li et al. 2015)
Fig. 8 Schematic depiction of the preparation of silica-based IIPs toward Co (II) ions (Reproduced
with permission from Liu et al. 2015a)
(Fig. 8). The prepared core-shell IIP showed high affinity and selectivity toward
Co2+ ions. The maximum Co2+ binding was achieved at pH 6.0.
Yin et al. prepared thiol-modified magnetic IIPs for selective extraction of Ag+
ions from wastewater (Yin et al. 2017). The prepared magnetic IIPs exhibited high
affinity and selectivity toward target Ag+ ions in the presence of other competing
ions such as Li+, Ni2+, Cu2+, and Co2+. The maximum binding capacity of IIPs
toward Ag+ was found as 35.47 mgg1.
In another study reported by Jiang and Kim (2014), Pt4+ imprinted polymer was
prepared by copolymerization of styrene and divnylbenzene in the presence of
functional monomers 4-vinylpyridine (4-VP) and dimethylglyoxime. The prepared
IIP displayed excellent binding selectivity toward Pt4+ ions in the presence of Ni2+,
Cu2+, and Pd2+. The highest Pt4+ binding was achieved within 40 min, and the
maximum binding capacity of IIP was 38.89 mgg1.
MIP-Based Molecular Traps for Solid Phase Extraction of Dye

Compounds from Environmental Samples
Textile, paper, rubber, food, and cosmetic industries commonly use dye compounds
(Hunger 2003; Kusic et al. 2013), and these compounds may lead to generation of
large volumes of contaminated effluents. The release of contaminated effluents into
the environment is a main source of environmental pollution that is a serious
problem all over the world. These contaminants must efficiently be removed from
the wastes which is a challenging task. Therefore, facile, efficient, low-cost, and
environmentally friendly methods are needed for this purpose.
Chemical and biological approaches are used for the removal of industrial dyes
from contaminated effluents. In biological processes, microorganisms such as fungi,
bacteria, algae, etc. have been used (Tan et al. 2013b; Gül 2013; Kelewou et al.
2014). Although this technique is low-cost and environmentally friendly, it is
challenging and not efficient. On the other hand, conventional materials such as
activated carbon are widely applied for the removal of dye compounds from
environmental samples (Hazzaa and Hussein 2015; Aguiar et al. 2016; Silva et al.
2016; Regti et al. 2017) due to its high adsorption capacity. However, activated
carbon has some drawbacks such as high-cost and regeneration problems.
MIP-based molecular traps can overcome these drawbacks. Recently, many
studies have been reported in the literature on the design and preparation of
MIP-based molecular traps for the removal of dye compounds from environmental
samples. In one of these studies, Kyzas et al. (2013) prepared chitosan and cyclo-
dextrin (CD)-based MIPs for the selective removal of Remazol Red 3BS (RR) dye
from aqueous solutions. The preparation of CD-based MIP toward RR schematically
depicted in Fig. 9. The effect of pH, time, and initial dye concentration on binding of
dye were also studied to determine the best conditions. The obtained results showed
that CD-based MIP exhibited higher binding behavior toward target dye compound
than chitosan-based MIPs. The maximum binding capacity was found to be as
35 mgg1. The selectivity experiments were also carried out and the results con-
firmed that the prepared MIPs showed great selectivity toward target dye RR in the
O CI O O
SO3Na S
NaO S N N O S ONa
O O O
N OH HN N N
H
N Dye
O TDI
NaO S SO3Na
O +
β-CD
Dye extraction
Dye rebinding
Desorption
Fig. 9 The preparation of CD-based MIP toward RR (Reproduced with permission from
Kyzas et al. 2013)
presence of other reactive dyes such as Remazol Yellow Gelb 3RS and Remazol
Brilliant Blue RN.
In another study, Li et al. prepared magnetic MIPs for the extraction of Rhoda-
mine B (RhB) dye from aqueous solutions (Li et al. 2017). For this purpose,
magnetic silica nanoparticles (Fe3O4@SiO2) were coated with MIP shell having
fluorophore nitrobenzoxadiazole (NBD). The results showed that a clear change in
fluorescent intensity was observed through fluorescence resonance energy transfer
(FRET) between the functional monomer and RhB dye (Fig. 10). Therefore, the
prepared MIP-coated magnetic silica nanoparticles also behave as a fluorescent
nanosensor toward the target compound RhB. The prepared MIP-coated magnetic
Fig. 10 The schematic representation of the preparation of magnetic MIPs toward Rhodamine B
(Reproduced with permission from Li et al. 2017)
silica nanoparticles were successfully applied for the recognition of RhB in aqueous
solutions. The maximum RhB binding was achieved in within 60 min, and
the maximum binding capacity of the magnetic nanoparticles was found to be as
29.64 mgg1.
Al-Degs and co-workers prepared MIPs toward Cibacron reactive red (CRR) dye
(Al-Degs et al. 2009). MAA and methyl methacrylate (MMA) were used as func-
tional monomers for the preparation of CRR imprinted polymers (MIP 1 and MIP 2).
The binding capacities of the prepared MIP 1 and MIP 2 toward CRR were 79.2%
and 38.2%, respectively. Furthermore, the obtained results from selectivity experi-
ments indicated that the prepared MIPs exhibited high selectivity toward target dye
compound CRR in the presence of other reactive dyes Cibacron reactive blue and
Cibacron reactive yellow.
In another research published by Asman et al., MIP was prepared for the
extraction of methylene blue from aqueous solutions (Asman et al. 2011).
MAA and EGDMA were used as the functional monomer and cross-linker, respec-
tively. The prepared MIP was successfully applied for the selective extraction
of methylene blue from aqueous solutions in the presence of methyl orange
and fast green. The maximum binding of methylene blue was achieved at pH 5.0
within 30 s.
Melvin et al. developed polysulfone membrane having TiO2 nanoparticles coated
with MIP and successfully used for the removal of methylene blue from aqueous
solutions (Melvin Ng et al. 2017). The prepared MIP-based composite membrane
showed high affinity and selectivity toward target dye compound in the presence of
methylene orange with a selectivity factor of 2.0.
Gao and colleagues prepared Sunset yellow-imprinted SiO2 particles using
acryloyloxyethyl trimethyl ammonium chloride as the functional monomer (Gao
et al. 2015). The obtained results showed that the prepared MIP-based SiO2 particles
exhibited excellent affinity toward the target compound Sunset yellow dye and the
maximum binding capacity was found to be 416 mgg1. The selectivity experiments
were also carried out in the presence of other azo dyes such as Acid red 14 and Acid
red 18. The selectivity coefficients of the MIP-based SiO2 particles for Sunset
yellow/Acid red 18 and Sunset yellow/Acid red 14 binary mixtures were 8.36 and
7.63, respectively.
Table 1 shows the micro- and nanostructured MIP-based traps for environmental
applications.
Conclusions
This chapter highlights the recent applications of MIPs as tailor-made selective traps
in extraction of pollutants such as such as pharmaceuticals, metal ions, and dye
compounds from environmental samples. In recent years, there has been growing
interest in SPE applications of MIP-based materials. The number of published
examples confirmed that MIPs with high affinity and selectivity toward target
compound(s) are effective and promising materials for the selective removal of
Table 1 Micro- and nanostructured MIP-based traps for environmental applications

Reference Composition of MIP-based trap Analyte Sample
Pharmaceutical compounds
Piacham et al. QCM sensor surface coated with MIP Propranolol Aqueous
(2005) layer using MAA as the functional solutions
monomer
Mirmohseni QCM sensor surface coated with MIP Methomyl Natural water
and layer using MAA as the functional
Houjaghan monomer
(2013)
Singh and QCM sensor surface coated with MIP Melphalan Aqueous
Singh (2015) layer using 3-thiophene acetic acid solutions
(3-TAA) as the functional monomer
Niu et al. Magnetic core-shell MIPs prepared by Norfloxacin Pharmaceutical
(2017) using functional monomers MAA and wastewater
AAm
Zazouli et al. MIP particles prepared by using MAA Sulfathiazole Pharmaceutical
(2017) as the functional monomer wastewater
Lu et al. MIP film prepared by using functional Pazufloxacin Aqueous
(2017) monomer MAA on the capacitive mesylate solutions
sensor surface
Manzo et al. MIP particles prepared by using Diclofenac and Waste water
(2015) 1-vinylimidazole as the functional mefenamic acid
monomer
He et al. Magnetic MIP nanoparticles prepared Dienestrol Seawater
(2016b) by using functional monomer MAA
Zhang et al. ZnS coated by MIP film layer using Ciprofloxacin Aqueous
(2012) MAA as the functional monomer solutions
Bitar et al. MIP having methacrylamide as the Iprodione Aqueous
(2017) functional monomer solutions
Du et al. MIP having MAA as the functional Difenoconazole Tap water
(2014) monomer
Kubo et al. MIP having MAA as the functional Sulpiride River water
(2014) monomer
Chen et al. MIP having MAA as the functional Sulfonamides Lake water
(2013) monomer
Metal ions
Hashemi and Rb (I) imprinted nanoparticles having Rb (I) Aqueous
Shamsipur dibenzo-21-crown-7 as the ligand solutions
(2016)
Monier and Au (III) imprinted polymer-chitosan Au (III) Aqueous
Abdel-Latif composite modified with SH groups solutions
(2017)
Xi et al. Cd (II) imprinted polymer having Cd (II) Wastewater
(2015) dithizone-Cd (II) complex
Preetha et al. (UO2)(II) imprinted polymers having (UO2)(II) Nuclear power
(2006) functional monomer 4-VP reactor effluents
(continued)
Table 1 (continued)
Reference Composition of MIP-based trap Analyte Sample
Liu et al. Graphene-SiO2 composite having Ni Ni (II) Aqueous
(2015b) (II) imprinted polymer having solutions
functional monomer acrylamide
Behbahani Pb (II) imprinted nanoparticles having Pb (II) Aqueous
et al. (2015) functional monomer 4-VP solutions
Büyüktiryaki CH3Hg (I) imprinted beads having CH3Hg (I) Aqueous
et al. (2007) MAC as the functional monomer solutions
Liu et al. Sr (II) imprinted polymer-chitosan Sr (II) Aqueous
(2015c) composite having dithiocarbamate solutions
Kalal et al. Ion imprinted aniline/formaldehyde Ir (III) and Aqueous
(2013) resin Pd (II) solutions
Say et al. CN imprinted polymer having CN () Aqueous
(2004) MAH-Ni(II) as the complex monomer solutions
Fasihi et al. Silica particles grafted with (UO2) (UO2)(II) Aqueous
(2016) (II) imprinted polymer solutions
Khoddami and Magnetic MIPs having functional NH Co (II) Aqueous
Shemirani groups solutions
(2016)
Chen et al. Ion imprinted magnetic chitosan Ni (II) Aqueous
(2016) composite solutions
Kong et al. Cr(VI) imprinted nanoparticles having Cr (VI) Aqueous
(2014) functional monomer 4-VP solutions
Hou et al. Ag (I) imprinted hollow particles Ag (I) Aqueous
(2015) having glycidyl methacrylate as the solutions
functional monomer
Dye compounds
Franco et al. Magnetic molecularly imprinted Disperse Aqueous
(2017) polymer having acrylonitrile as the Red 73 solutions
functional monomer
Deng et al. MIP-chitosan composite having Ti (IV) Active Brilliant Aqueous
(2017) Red X-3B solutions
Foguel et al. MIP having 1.vinylimizadole as the Acid green 16 Textile effluent
(2017) functional monomer and tap water
Lu et al. Molecularly imprinted membrane Rhodamine B Lake water
(2015) having functional monomer MAA
Lian and MIP having functional monomer MAA Malachite Seawater
Wang (2012) green
Ziru and MIP having functional monomer MAA Crystal violet Seawater
Jiangtao
(2014)
Kyzas et al. MIP having functional monomer AAm Reactive red Aqueous
(2009) MIP having functional monomer MAA Basic red solutions
undesired compounds from environmental matrices such wastewater. Furthermore,

these tailor-made materials can potentially be applied for large-scale extraction
processes.
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Removal of Pharmaceutically Active
Compounds from Contaminated 37
Water and Wastewater Using
Biochar as Low-Cost Adsorbents,
An Overview

Mohd Adib Mohammad Razi, and M. K. Amir Hashim
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 952
Removal of PhACs from Water and Wastewater by Filtration Membrane . . . . . . . . . . . . . . . . . . . . 952
Removal of PhACs from Water and Wastewater by Adsorption Process . . . . . . . . . . . . . . . . . . . . . . 953
Biosorption of PhACs by Microorganisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 958
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 958
Abstract
Pharmaceutically active compounds (PhACs) have received high attention during
the last few years due to their ability to persist for long time in the environment as
well as their role in increasing the antimicrobial resistance among the floral
bacteria in the nature. Many of the technologies have been investigated and
applied to remove those compounds from the contaminated water and wastewa-
ter. The most common technology depends on the oxidation process which leads
to degrade these compounds to be in inactive form. However, the oxidation
process has some challenges which lie in the presence of secondary products
and toxic by-products. The adsorption process is the best alternative technology
A. Al-Gheethi (*) · R. Mohamed · M. A. M. Razi · M. K. Amir Hashim

Micro-Pollutant Research Centre (MPRC), Department of Water and Environment Engineering,
Faculty of Civil and Environmental Engineering, University Tun Hussein Onn Malaysia (UTHM),
Parit Raja, Johor, Malaysia
e-mail: adel@uthm.edu.my
E. A. Noman
Faculty of Applied Sciences and Technology (FAST), Universiti Tun Hussein Onn Malaysia,
Pagoh, Johor, Malaysia

https://doi.org/10.1007/978-3-319-73645-7_25
952 A. Al-Gheethi et al.
where no energy is required and no toxic by-products are generated, and the
process leads to separate the pollutants from the water and wastewater. In this
chapter, the adsorption of PhACs by low-cost materials such as biochar and
microorganisms is discussed.
Keywords
Biochar · Bacteria · Adsorptive capacity · Efficiency
Introduction
One of the main pollutants in the water and wastewater which has high concerns by
the researchers is the xenobiotic organic compounds (XOCs) which included
endocrine-disrupting compounds (EDCs), disinfection by-products (DBPs), and
pharmaceutically active compounds (PhACs), since these compounds have high
persistence in the environment and can be transmitted through the water into the
food and then into the animals and human. Some of these compounds have high risk
health because they are synthesized in the laboratories and applied extensively as
antimicrobial agents or as growth inducers. The concepts of XOCs have occurred in
the 1990s due to the developments of the GC-MS and LC-MS techniques which
have high accuracy to detect the concentration of XOCs even at very low concen-
trations (PPM). Moreover, antibiotics which are group of PhACs represent the most
concern even at very low concentration due to their ability to induce the antimicro-
bial resistance among the bacteria in the natural water system. The high distribution
of resistant bacteria in the environment and water system creates great issues
especially when they are transmitted through the food chain into the human.
Recently many of the pathogenic bacteria have exhibited high resistance for several
types of the antibiotics. Indeed, it has to mention that most of the studies conducted
on the removal of PhACs have been reported in the developed countries, with very
few studies have been reported in the developing countries due to the absence
of advanced technology. Moreover, there are no specific legislations and regulation
for the presence of the PhACs in the wastewater disposed into the environment.
The current chapter highlighted the most common removal of PHACs using adsorp-
tion process.
Removal of PhACs from Water and Wastewater by Filtration

Membrane
There are several technologies have been investigated to remove PhACs from the
water and wastewater, the most common are the degradation process (chemical and
biological oxidation) and adsorption process (natural and biological adsorbents).
The filtration membrane is one of the efficient technologies to separate these
compounds from the water. Kimura et al. (2003) examined the efficiency of
37 Removal of Pharmaceutically Active Compounds from Contaminated Water. . . 953
nanofiltration (NF) and reverse osmosis (RO) membranes for removing PhACs
based on the adsorption of these compounds on the physicochemical structure of
the filter media. The study found that the filtration achieved >90% of the removal
regardless of physicochemical properties of the tested compounds; the removal
process takes place as a result of electrostatic exclusion. Therefore, the
non-charged compounds were less removed (<90%). The removal process for the
charged compounds has not depended on the time, while this factor and the molec-
ular size play an important role in the removing of non-charged compounds. One of
the limitations for the filtration process was the concentration of the PhACs, where
the removal percentage of these compounds with low concentration ranges (ng/l)
were less than that presented with high concentration ranges (μg/l). Therefore, the
application of the filtration process to remove PhACs depends on their concentration
in the water or wastewater.
Comerton et al. (2007) investigated the potential of nanofiltration (NF), ultrafil-
tration (UF), and reverse osmosis (RO) membranes to adsorb different types of the
PhACs, which included acetaminophen, carbamazepine, and gemfibrozil, from
water and wastewater. The study revealed that the adsorption process depended on
the compound water solubility. The maximum adsorption was recorded by UF
membrane followed by the NF and RO membranes. The adsorption process has
not correlated with the temperature which does mean that the filtration process has
the potential to be applied in any place regardless of the environmental condition.
The results also revealed that the adsorption process relied on the competition
between the target PhACs and the organic matter presented in the water and
wastewater, which might has more affinity to adsorb on the filter component.
McCallum et al. (2008) used polyamide thin-film composite nanofiltration
(NF) membranes for removing of 17β-estradiol (E2) based on the adsorption to the
membrane. The batch isotherm studies which were performed based on the filtration
experiments with intermediate stage products (e.g., membrane without polyamide
film coat) indicated that the adsorption processes for E2 appeared predominantly at
the polysulfone support layer, not at the polyamide active layer, as a result of
hydrophobic interaction. The main factors influenced on the adsorption of E2 were
pressure and water quality parameters which included pH and organic matters.
Removal of PhACs from Water and Wastewater by Adsorption

Process
The adsorption process is one of the extensive techniques which has been used to
remove the pollutants from the water and wastewater. The process depends mainly
on the presence of active site in terms of functional group on the surface of adsorbent
which reacted physically with the pollutants and removes it from the liquid phase
onto the surface of solid phase (adsorbent). The adsorption process is a common
method for removing of heavy metals and dyes; however, little work has been
performed on the removal of PhACs by this process. In this section the most
common adsorption process using low-cost adsorbents is reviewed. Kyzas et al.
(2013) synthesized new modified chitosans (Cs), grafted with sulfonate (CsSLF) or
N-(2-carboxybenzyl) groups (CsNCB) and cross-linked with glutaraldehyde and
tested for determining their efficiency in adsorbing PhACs (pramipexole
dihydrochloride (PRM)) from polluted water matrices. The effect of pH and
temperature on the adsorption of PRM was also investigated. The study found
that the optimum for the adsorption process was detected at pH 10. The isotherm
studies revealed that both initial PRM concentration and temperature affected
significantly the adsorption process. The adsorption rate followed the order:
CsSLF > CsNCB > Cs.
The potential of silica zeolites (Y, mordenite, and ZSM-5) with pore opening
sizes to adsorb sulfamethoxazole sulfonamide antibiotic was examined by Blasioli
et al. (2014). The study investigated the removal process in the water and studied
the effect of the temperature on the adsorption process. The results revealed that
the zeolite Y and MOR exhibited fast and efficient removal of sulfamethoxazole
(100%), while the kinetic adsorption by ZSM-5 associated with the temperature
where the removal efficiency increased with the increasing of temperature indi-
cating that the removal was a thermodynamic process. The analysis for the silica
zeolites showed that the sulfamethoxazole sorption was incorporated and localized
alongside the medium-weak and cooperative host-guest into the pore of each
zeolite system, which means that the water molecules play a certain role only in
zeolite Y and mordenite.
One of the low-cost materials with high efficiency to adsorb PhACs is the biochar
(BC), which is produced from the pyrolysis process for the carbon-rich biomass. It
has high application as a soil amendment as well as sorption of organic compounds
in the amended soil due to the high surface activity (Jha et al. 2010). The ability of
biochar to adsorb the PhACs such as antibiotics has been reported in the literature;
the high efficiency belongs to the interaction between the aromatic rings on the
PhACs and biochar (Hurtado et al. 2017). However, the authors claimed that the
efficiency of biochar to adsorb PhACs is influenced by humic acid (HA) dependent
on the properties of BC, sorbate, and adsorbed HA (Guo et al. 2007; Duan et al.
2017). Lian et al. (2015) investigated the effect of loaded humic acid (HA) in two
different modes including pre-coating and co-introduction with sorbate on biochar
sorption for sulfonamides. The study revealed that the effect of HA on the sorption of
sulfonamides by BC relied on the nature of interaction between HA fraction and
sorbate as well as the HA concentrations.
Nevertheless, it has to mention that the efficiency of the biochar in the
adsorption process is less than the activated carbon due to the low porous
available on the less surface area, which are the critical factors in the
adsorption process (Falco et al. 2013). Therefore some of the authors have
shifted to make a modified particles of biochar to improve the adsorption
capacity. An advanced work on the biochar was conducted by Shan et al.
(2016). In this study the biochar was prepared in an ultrafine magnetic
particles biochar by using ball milling. The ultrafine magnetic particles of
biochar were prepared as a magnetic biochar/Fe3O4 and activated carbon
(AC)/Fe3O4. Thereafter, both materials were used for carbamazepine (CBZ) and
tetracycline (TC) removal by adsorption and mechanochemical degradation. The

study revealed that the biochar/Fe3O4 exhibited 62.7 mg/g for CBZ and 94.2 mg/g
for TC of the adsorptive capacity, while AC/Fe3O4 achieved 135.1 mg/g for CBZ
and 45.3 mg/g for TC, respectively. The investigation for the effect of pH on the
adsorption process indicated that the removal of TC was dependent on the pH of
the solution, while adsorption of CBZ was independent. In the study for the
degradation of the adsorbed compounds, the study claimed that TC degraded by
97% within 3 h, while only 50% of the CBZ was degraded in the same period. In
the study, the authors examined the addition of quartz sand during the preparation
of BC and found that the presence of the sand enhanced the mechano-
chemical degradation of CBZ on biochar/Fe3O4 to 98.4% with 0.3 g quarts sand/g
adsorbent.
Zhang et al. (2016) synthesized a novel carbonaceous nanocomposite for
sulfamethazine (SMT) sorption. The adsorbent was synthesized by pyrolysis of
dip-coating straw biomass in carboxyl functionalized multiwalled carbon nanotube
solution at 300 C and 600 C in air condition. The preparation method used here
was effective for producing high sorption capacity materials. The carbonaceous
nanocomposites were also mixed with the soil to understand the influence of the
soil/biological and chemical aging on the adsorption process, and the results found
no effect on the SMT sorption. The author explained the sorption mechanism based
on the van der Waals forces as well as the hydrogen bonding and electron-donor-
acceptor interaction. Based on this study, it was concluded that the carbonaceous
nanocomposites have potential in removal of PhACs from the contaminated water
and wastewater.
Zhang et al. (2011) used the corn straw biochars (CSB) as adsorbent for simazine;
the CSB was prepared at temperature ranging from 100 C to 600 C. The adsorption
process was explained based on the characteristics of biochars determined by
BET-N2 surface area (SA), 13C NMR, and FTIR, while the isotherms of adsorption
were studied with Freundlich and dual-mode models. The study revealed a positive
correlation between log Koc values and aromatic C contents of the simazine, while
exhibited a negative correlation with (O + N)/C ratios. These results indicated that
the aromatic-rich biochars have high-binding affinity to simazine. The dual-mode
model results claimed that the adsorption capacity of biochar is dependent on the
carbonization degree. Therefore, the corn straw biochars prepared at high tempera-
ture can effectively adsorb the simazine.
Ncibi and Sillanpää (2017) conducted several experiments on the removal of
dorzolamide (DA) and carbamazepine (CZ) from artificially contaminated waters
by adsorption process using as-synthesized multiwalled carbon nanotubes (intermit-
tently MWCNTs or CNTs) and mesoporous activated carbons (Meso-AC). The
optimization process was determined based on four factors which included solution
pH, temperature, the application of ultrasonication, and exposure time. The study
revealed that the efficiency of the adsorption process depended on the porous
structure of the materials. The optimum removal process was noted at pH between
6 and 8. Moreover, the ultrasound process has enhanced the removal capacities of
PhACs investigated in this study. Based on the Brouers-Sotolongo equation analysis,
the isotherm model detected 99.5–99.9% of the removal efficiency. The maximum
adsorptive capacity of MWCNT was 224.6 mg/g for CZ and 78.8 mg/g for DA; this
capacity is higher than that reported for other adsorbents. However, it’s still less than
that recommended by (Gadd 1990) where the minimum absorptive capacity should
be more than 150 mg/g to be competitive with other technology.
Lin et al. (2017) examined the effect of salts and organic matter on the
efficiency of biochar and an activated carbon in removing ibuprofen and sulfa-
methoxazole from reclaimed water reverse osmosis (RO), synthetic and concen-
trate solutions spiked with selected organic compounds, as well as nontarget water
constituents (trace elements, humic acid (HA), alkalinity, and bovine serum
albumin (BSA)). The kinetic modeling studies were performed to explain the
role of water composition on the adsorption process of PhACs. The study appeared
that the adsorption capacity of biochar depended on the physicochemical proper-
ties such as ash content, specific surface area, charge, pore volume, as well as
hydrophobicity, π-energy, and speciation of pharmaceuticals. The adsorption
process was pH dependent; therefore, the removal efficiency associated with the
elevation of pH value as a response for the formation of electrical interactions
between ibuprofen and sulfamethoxazole and biochar, and for the same reason, the
high salt contents improved the removal process, while HA and BSA reduced the
adsorption capacity of biochar.
Biosorption of PhACs by Microorganisms
The utilization of microorganism in the biosorption process has been inves-

tigated extensively by many of the authors in the literature. Most of those studies
have been performed for heavy metal removal. The microorganisms which
included bacteria, fungi, and microalgae have a novel cell wall structure which
enables them to be attractive in the biosorption technique. The cell surface of the
microorganisms has several functional groups such as hydroxyl, carboxyl, phos-
phate, and lipids which have a negative charge and can easily attract the positive
charge pollutions such as heavy metals. However, few studies have been
conducted in the using of microorganism cells to removal of PhACs based on
the biosorption process. Al-Gheethi et al. (2014) investigated the potential of
bacterial cell biomass (living and dead cells) to remove cephalexin antibiotic
from the secondary effluents. In the study the bacterial cells were treated by
autoclave (110 C for 10 min) and then used for the removal of cephalexin. The
results revealed that the maximum biosorption capacity was 60 mg cephalexin
g1 cells. Moreover, this efficiency has reduced by 40.83% and 82.88% (living
and dead cells, respectively) in the presence of heavy metals such as Ni2+ in
comparison with the control. In contrast, the biosorption by dead cell biomass
was undetectable in the presence of Cd, Zn, Cu, and Pb ions, indicating the less
affinity of cephalexin to the bacterial cells in comparison with the heavy metals.
Moreover, in another study Al-Gheethi et al. (2017) used consortium bacterial
cells to remove cephalexin from the aqueous solution. The factors affecting the
removal process which included cephalexin concentrations, biomass concentra-

tion, pH, temperature, and time were tested. In the study the bacteria species were
subjected for the adaption process to tolerate the cephalexin in order to increase the
biosorption capacity. The results revealed that the maximum biosorption effi-
ciency was recorded at low concentrations of cephalexin (94.73% vs. 92.98%
for living and dead cells, respectively). The dead cells have more capacity to
adsorb the cephalexin than the living cells at high concentrations of cephalexin.
The optimum pH was determined between pH 4 and 6 (71.95–68.90%), while the
adsorption process was more efficient at 25 C and 30 C. However, similar
findings were also noted in this study where the affinity of cephalexin is reduced
in the presence of heavy metals. The most common microorganisms which are
used for biosorption of PhACs are presented in Table 1.
Table 1 Biosorptive capacity of some types of biomass to remove antibiotics (Adopted from
Al-Gheethi et al. 2015)
Biosorptive
Biomass Antibiotic capacity (Qmax) References
R. arrhizus Penicillin G 459.0 mg g1 Aksu and
Tunç (2005)
Active carbon Amoxicillin 200 mg g1 Budyanto
et al. (2008)
Activated sludge Tylosin 7.7 mg g1 Prado et al.
Tetracycline 72 mg g1 (2009)
Multiwalled carbon nanotubes Cephalexin 1100 mg g1 Jafari et al.
(CNTs) Cefixime 820 mg g1 (2011)
Granular Penicillin 427.3 mg g1 Liang (2011)
Activated carbon (GAC) Ampicillin 164.2 mg g1
Cephalosporin 33.67 mg g1
Graphene oxide (GO) Tetracyclines 313 mg g1 Gao et al.
(2012)
Sludge biochar Fluoroquinolone 19.80 mg g1, Yao et al.
(2013)
Biocomposite fibers of graphene Ciprofloxacin 18.45–39.06 mg/g Wu et al.
oxide/calcium alginate (2013)
B. subtilis 1612WTNC (living cells) Cephalexin 35.02 mg g1 Al-Gheethi
B. cepacia 103WTC (dead cells) 40.74 mgg1 (2014)
Mixed Gram-positive bacteria (living 50.91 mgg1
cells)
Mixed Gram-negative bacteria 40.44 mgg1
(living cells)
Mixed Gram-positive bacteria 15.99 mgg1
(dead cells)
Mixed Gram-negative bacteria 25.11 mgg1
(dead cells)
Mixed bacterial biomass 60 mgg1
(living cells)
Conclusion
It appeared that many of the low-cost materials have been used for the removal of
PhACs. However, the main challenges lie in the less affinity of these compounds to
be adsorbed on the surface of the adsorbent. Moreover, the preparation of biochar at
high temperature might improve their ability to be much better than activated carbon
in removing of PhACs. Biochar represents one of the most alternative materials for
the activated carbon. The potential of microorganisms in the biosorption of PhACs
has less investigations. However, the most potent microorganisms might be mixed
with the biochar to increase the surface area of the biochar and then enhance the
adsorption efficiency. More work is needed for getting an efficient adsorbent for
removal of PhACs from the contaminated water and wastewater.
Cross-References
▶ Development In-House: A Trap Method for Pretreatment of Fat, Oil, and Grease in
Kitchen Wastewater
▶ Microbial Risk Associated with Application of Biosolids in Agriculture
▶ Treatment of Domestic Gray Water by Multicomponent Filters
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Microbial Risk Associated with
Application of Biosolids in Agriculture 38
Abd. Halid Abdullah, and M. K. Amir Hashim
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 962
Biosolid-Borne Bacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 963
Risk Assessment of Pathogenic Bacteria in Soil Fertilized with Biosolids . . . . . . . . . . . . . . . . . . . . 967
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 968
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 968
Abstract
The present chapter aimed to highlight the pathogenic risk associated with the
application of biosolids in agriculture. The main pathogens and their health impor-
tance as well as their ability to survive and be transmitted into humans through the
food chain have been discussed. It has appeared that the direct utilization of
biosolids in agriculture represents one of the main sources of human and animal
infections due to the ability of most pathogens to survive in the environment.
Therefore, the biosolids should be subjected to further treatment process in order to
A. Al-Gheethi (*) · R. Mohamed · M. K. Amir Hashim

e-mail: adel@uthm.edu.my
E. A. Noman
Faculty of Applied Sciences and Technology (FAST), Universiti Tun Hussein Onn Malaysia,
Pagoh, Johor, Malaysia
A. H. Abdullah
Micro-pollution Research Centre (MPRC), Department of Water and Environmental Engineering,
Faculty of Civil and Environmental Engineering, Universiti Tun Hussein Onn Malaysia, Batu,
Pahat, Malaysia

https://doi.org/10.1007/978-3-319-73645-7_26
reduce the pathogen level to less than the health risk which lies in the elimination of
these pathogens or minimize their ability to regrow in the environment.
Keywords
Pathogenic bacteria · Reuse · Sludge · Agricultural purpose
Introduction
One of the most important and challenging steps in sewage treatment systems is the
disposal process of the generated sludge due to high contents of organic matter,
heavy metals, as well as pathogenic entities such as bacteria, viruses, protozoa, and
helminths (Al-Gheethi et al. 2013). The stricter regulations adopted by several
countries on the disposal of sewage into landfill, high costs of chemical fertilizers,
and their toxicity on human health have increased interest in the reuse of sludge in
the crop production. The sludge consists of organic matter and is rich with nutrients
which play an important role in increasing soil fertilization. In contrast, the sludge is
rich with high diversity of bacteria and heavy metals that might have adverse effects
on crop production and human health. Therefore, before the reuse of sludge as
fertilizers, it must be treated to remove the remaining putrescible material as well
as enteric bacteria to prevent the danger of spreading enteric diseases.
The management of the ever-increasing volume of the sludge has been one of the
prime environmental issues in several counties. However, developing countries have
yet to adopt a practical, economic, and acceptable approach in managing and dispos-
ing sludge. The amount of sludge resulted from sewage treatment plants (STPs) have
been increasing at a rapid pace in recent years due to the high increase in population
equivalent. The human wastes have drawn serious attention from the society
(Cheremisinoff 1994). In Malaysia, 2.97 billion m3 of sewage sludge is produced by
Indah Water Konsortium (IWK) annually; this sludge volume is expected to rise to
7 million cm3 by the year 2020 (Azman and Shaari 2013). However, there is no
information on the reuse of sludge in crop production as the Government of Malaysia
has yet to have a policy on the reuse of sludge for agriculture purposes (Azman and
Shaari 2013). In the European Union (EU), the total quantity of produced sludge
increased from 7.2 million tons of dry matter in 1998 to 9.8 million tons in 2009, about
37.0% of these sludges was used for agriculture, and the worldwide production of
sludge is estimated in limits of 20 billion tons annually (Evans 2012).
Many disposal methods are applied for the sludge including ocean dumping,
incineration, spreading on agricultural land, soil incineration, land spreading in
forestry, or landfilling (Supakata and Chunkao 2011). The most common practice
of sludge in developing countries is disposal to landfill. However, in EU, these
practices have reduced from 40% in 1994 to 17% in 2005. In 2009 only 1% of sludge
was disposed into the landfill. These reductions were due to the presence of strict
standards relating to landfill of biodegradable waste (Holt et al. 1995). Land appli-
cation of sludge has several benefits for plants which include supplying nutrients
(nitrogen, phosphorous, and trace elements) to crops. The application of sludge as
fertilizers might improve the soil physical properties because sludge typically
38 Microbial Risk Associated with Application of Biosolids in Agriculture 963
possesses excellent soil amendment properties and increases soil organic matter
content (Hamouda and Abu-Shaaban 2014). Alongside, biosolids contain constitu-
ents that may pose a risk to soil, water, plants, animals, or public health. The
concerns lie in the heavy metals, soluble salts, and other trace constituents which
pose serious concerns and can damage soils, plants, animals, and humans as well as
the potential for disease transfer by high pathogen diversity in the sludge.
There are many sources of biosolids such as those generated from animals or
poultry wastewater. However, this review focused only on biosolids resulted from
human sewage. In this review, the health risk of human associated with reuse
biosolids in the agriculture are discussed based on the pathogenic bacteria. This
work will focus on the adverse effects of pathogenic bacteria on humans and plants
and the possibility to accumulate these pollutants in land fertilized with the biosolids.
Biosolid-Borne Bacteria
Microorganisms in raw sewage are transmitted to biosolids due to the stabilization

and sedimentation process of sewage treatment system, in which bacterial cells are
adsorbed on the solid materials and then precipitate with these materials (Strauch
1991, 1998). US EPA (2003) revealed that the pathogens in the domestic sewage are
primarily associated with insoluble solids. These organisms become bound to solids
following wastewater treatment and are transferred to biosolids. Hence, the biosolids
have higher quantities of pathogens than wastewater (Al-Gheethi et al. 2014).
However, it is important to indicate that not all bacteria in biosolids are considered
harmful, since many different organisms live within the sewage itself, assisting in the
decomposition of organic pollutants. These organisms also helped to convert the raw
sewage into biosolids to become incorporated into a Class A or B biosolids (Gerba
and Smith 2005). In this section, the adverse effect of pathogenic bacteria in sludge
for plants and human will be discussed based on the potential to survive in the
environment and the pathogenicity for human and plants.
Biosolids contain different diversity and density of pathogenic bacteria depending
on the treatment process efficiency used in sewage treatment plants (STPs). Further,
raw and untreated biosolids contain significantly higher diversity and density of
pathogens than secondary and treated or dried biosolids (Al-Gheethi et al. 2014). The
quality of biosolids depends on the health of the population contributing to STPs,
and as the health of the population varies from one time to another, the characteristics
of biosolids also vary (Harrison et al. 1999). Therefore, occurrences of pathogenic
organisms in biosolids in infected population communities even in the small com-
munity are more frequent than in the large communities (US EPA 2002); the quality
of biosolids also varied geographically and seasonally at the same STPs.
The nature of biosolids as human wastes always causes a hygienic risk in storage,
collection, processing, handling, and utilization. Straub et al. (1993) reported that the
raw sludge might release airborne pathogens more than the treated ones. Therefore,
strict regulations for hygienic principles must be applied during the storage, transport,
and distribution of these wastes (Martens et al. 1998). The basic hygienic risk is the
occurrence of pathogens in biosolids which represents the starting point
for understanding the epidemiological reflections and necessary precautions (Strauch

1991).
There are three types of health risks related to the presence of pathogenic bacteria
in biosolids which have to be considered during the reuse of biosolids in agriculture.
These risks included occupational health risks, risks concerning product safety,
and environmental risks (Strauch 1998). According to US EPA (2007), biosolids
generated from STPs are classified into Class A and B based on microbio-
logical characteristics. In Class A, fecal coliform (FC) bacteria should be less than
1000 cell/g of dry wt, and Salmonella spp. are less than 3 cell/25 g of dry
wt. In Class B, FC are more than 1 million/g of dry wt, while no criteria are required
for Salmonella spp. Therefore, the utilization of biosolids in the agriculture depends
on the class of biosolids. In class A, biosolids can be utilized as fertilizers of soils used
for crop production. In contrast, the soil amended with class B should be exposed to
sunlight for at least 1 year before utilization for agriculture in which the pathogenic
bacteria in biosolids would be reduced to be less than the risk level (US EPA 2003).
Pathogenic bacteria in biosolids reused for agriculture can be divided into two
groups: plant pathogenic bacteria and human pathogenic bacteria. Plant pathogenic
bacteria are those released from the vegetable wastewater. These pathogens grow at
ambient environmental temperature; therefore, the sewage treatment processes
performed at mesophilic temperature might be enough to reduce their concentra-
tions. In the term of human pathogenic bacteria, a wide range of pathogen and
opportunistic pathogens have been reported in biosolids. The most significant
pathogenic bacteria in biosolids include Campylobacter jejuni, enteropathogenic
E. coli, Leptospira spp., Salmonella spp., Shigella spp., Vibrio cholerae, Listeria
monocytogenes, Staphylococcus aureus, and Yersinia spp. (Straub et al. 1993; US
EPA 1994; Viswanathan and Kaur 2001). Acinetobacter spp., Alcaligenes spp.,
Flavobacterium spp., Pseudomonas spp., and Zoogloea spp. have been also reported
as predominant in biosolids (Kappesser et al. 1989; Wen et al. 2009). The pathogenic
bacteria in biosolids include Aeromonas hydrophila, Acinetobacter cloaca, Bacillus
anthracis, E. coli, Campylobacter spp., Clostridium botulinum, C. perfringens,
diphtheroid spp., Edwardsiella spp., Enterobacter spp., Flavobacterium spp.,
Hafnia spp., Klebsiella spp., Leptospira spp., Listeria monocytogenes, Mycobacte-
rium tuberculosis, M. bovis, Proteus spp., Providencia spp., Pseudomonas
aeruginosa, Salmonella paratyphi, S. typhimurium, Sarcina spp., Serratia spp.,
Shigella spp., Staphylococcus spp., Vibrio cholerae, and Yersinia enterocolitica
(Straub et al. 1993; Viswanathan and Kaur 2001; Al-Gheethi et al. 2014). Ashbolt
et al. (2001) found Pseudomonas, Streptococcus, Flavobacterium, and Aeromonas
species (called opportunistic pathogens) in biosolids. Markosyan et al. (2002)
indicated that among several species of opportunistic bacteria in biosolids, Klebsi-
ella pneumonia, K. oxytoca, Enterobacter, Hafnia, Serratia, Proteus, and Pro-
videncia are the most prevalent. Ibekwe and Grieve (2003) revealed that the
dominant bacteria in biosolids are related to Bacillus, Clostridium, Mycoplasma,
Eubacterium, and Proteobacteria which are originally retrieved from the gastroin-
testinal tracts of mammals.
The bacterial diversity in the biosolids varied from one region to another,
depending on the treatment process, for instance, Urdaci et al. (1991) isolated
2–39% of bacteria from biosolids at Spain, and these bacteria were identified within
23 species of Vibrio. Autheunisse and Koene (1987) indicated that Acinetobacter
spp., Pseudomonas spp., Aeromonas spp., and Flavobacterium spp. are more com-
mon in the biosolids generated from aerobic treatment process.
The predominantly foodborne in biosolids include Arcobacter spp., Bacillus
cereus, C. coli, C. jejuni, C. perfringens, Campylobacter fetus, Clostridium botuli-
num, E. coli O111:NM, E. coli O104:H21, Escherichia coli O157:H7, Listeria
monocytogenes, S. enteritidis, S. typhimurium, Salmonella typhi, Shigella sp., Staph-
ylococcus aureus, V. parahaemolyticus, V. vulnificus, Vibrio cholerae O1, and
Y. enterocolitica (Dumontet et al. 2001; Stampi et al. 1999).
In general, the pathogenic bacteria in biosolids can be divided into major and
minor concerns based on their significance to human health as stated by Dudley et al.
(1980) and Kowal (1983). Salmonella sp., Shigella sp., Vibrio cholerae, E. coli
(pathogenic strains), Campylobacter jejuni, Leptospira sp., and Yersinia
enterocolitica are classified within the major concern, while Aeromonas sp., Clos-
tridium perfringens, Pseudomonas aeruginosa, and Staphylococcus are classified
within the minor concern category. In some literature, the pathogenic bacteria in
biosolids are classified as primary and opportunistic pathogens.
The most important pathogenic bacteria are those transmitted by the fecal-oral
route, as they have already acclimated to infect and grow at the human temperature
(US EPA 2003). Enteric pathogenic bacteria within biosolids represent a highly
diversified group due to the presence of high contents of nutrients. For instance,
E. coli strains which is one of the main enteric bacteria in biosolids are composed of
Shiga toxin-producing E. coli (STEC) and enterohemorrhagic E. coli (EHEC) asso-
ciated with potable and recreational water (Kaper et al. 2004). However, non-enteric
pathogenic bacteria which included Legionella spp., Mycobacterium spp., Leptospira
spp., and Pseudomonas spp. have also been detected in biosolids (Toze 1997).
The most attention in terms of risk to human health is Salmonella and E. coli
O157:H7. Both bacteria have been isolated by many authors in the literature (Dudley
et al. 1980; Droffner and Brinton 1995; Hoeller et al. 1999; Sahlström et al. 2004).
According to WHO (1981), Salmonella spp. are the most relevant species in bio-
solids. However, the risk of this bacterium to humans is associated with the food
animal which acts as carriers of salmonellosis as a result of grazing in pastures or fed
crops grown on biosolid-amended fields. In Denmark, biosolids are considered
Salmonella-positive when WWTP received sewage sludge from more than 4000
people (Larsen 1998). Burtscher and Wuertz (2003) indicated that Salmonella spp.
were detected by 48% of the 46 biosolid samples collected during intermediate
stages of biosolid treatment process. Lucero-Ramirez (2000) reported that Salmo-
nella are pathogenic bacteria of major concern in biosolid management, primarily
when biosolids are considered for land disposal. Dumontet et al. (2001) revealed that
Salmonella spp. are the most widespread bacterial pathogens of significant global
public health concern that are likely to cause an important biosolid contamination.
S. senftenberg is one of the Salmonella spp. which have been associated with
consumption of raw foods that have been fertilized or in contact with poultry wastes
(Taormina et al. 1999). According to US EPA (2003), Salmonella spp. are bacteria of
great concern as well as good representatives of reduction of other bacterial
pathogens due to their abundant with higher densities in biosolids and ability to
survive for the reduction process of pathogens in biosolids. S. senftenberg has been
suggested as it is relatively heat resistant but rarely affects humans. S. stanley was
the only pathogen isolated after the thermophilic anaerobic digestion (Sahlström
et al. 2004).
Among 2000 serotypes of Salmonella spp., two serotypes of Salmonella, S. typhi
and S. paratyphi (A, B, C), are most dangerous to people. The high pathogenicity
of Salmonella spp. is due to their ability to infect nearly all living vectors from
insects to mammals (Strauch 1991), besides the potential to resist a wide range of
antibiotics.
There are four species of Shigella spp. that have been isolated from biosolids.
However, S. dysenteriae is among the most common causes/sources of diarrhea in
humans. Yersinia spp. have isolated from anaerobically biosolids (Dudley et al.
1980). This bacterium excretes in feces and transmits by direct contact or food
poisoning. Moreover, the waterborne outbreaks are due to fecal contamination of
water. Aeromonas caviae is one of the dominant species in biosolids; this bacterium
is transmitted into human via water contaminated with biosolids, and thus it may be a
potential indicator of biosolid pollution (Ramteke et al. 1993). Aeromonas
hydrophila has also been noted in biosolids (Poffe and Beek 1991).
The importance of biosolids in the dissemination of L. monocytogenes in the
environment has been detected. The presence of L. monocytogenes has been reported
in biosolids (Sahlström et al. 2004) and on plants (Weis and Seeliger 1975),
including vegetables (Beuchat 1996). Besides, L. monocytogenes has been isolated
from contaminated surface water (Watkins and Sleath 1981). De Luca et al. (1998)
demonstrated that biosolids contain L. monocytogenes. The presence of
L. monocytogenes in biosolids was confirmed by De Luca et al. (1998) who tested
five different types of biosolids (primary raw, activated, thickened, digested, and
dewatered) in an Italian sewage treatment plant and revealed that L. monocytogenes
was detected in all biosolid types. Hence, L. monocytogenes should be considered as
a potential health risk in soil amended with biosolids. De Luca et al. (1998) also
demonstrated the presence of L. monocytogenes in biosolids. However, the occur-
rence of L. monocytogenes was correlated with the season as it was more abundant in
spring and autumn. The presence of L. monocytogenes in biosolids is due to their
ability to survive during the biological oxidation.
Campylobacter spp. have been isolated from biosolids; among the different
species, C. jejuni and C. coli are the most common (Sahlstrom et al. 2004; Bagge
et al. 2005). Stampi et al. (1999) indicated that Campylobacter spp. are available
only in untreated biosolids and are absent from the secondary biosolids. This is
because Campylobacter spp. are quite sensitive to mesophilic anaerobic digestion
(Stelzer and Jacob 1991). However, Kearney et al. (1993) revealed that C. jejuni
could still be detected even after 112 days of the storage period of biosolids treated
by mesophilic anaerobic digestion. Campylobacter are often connected with out-
breaks caused by fecal contamination of water (Gallay et al. 2006).
There are few reports which indicate the presence of Mycobacterium spp. in
biosolids. However, Dudley et al. (1980) and Pickup et al. (2006) isolated
unspecified Mycobacterium spp. from biosolids. Dailloux et al. (1999) isolated

M. tuberculosis from biosolids of swage coming from hospitals.
M. paratuberculosis has been found in biosolids in the United Kingdom (Pickup
et al. 2005). Clostridium spp. are present in anaerobically digested sewage sludge
(Dudley et al. 1980). Using digested residue as a fertilizer could contaminate the
silage, because neither anaerobic digestion nor ensiling inactivates C. tyrobutyricum
(Johansson et al. 2005).
Several factors affecting the potential of pathogenic bacteria from biosolids
to cause infection to human include the ability of the bacteria to survive in
the biosolids and environment, infective dose, and pathogenicity. With regard to
survival in the biosolids and environment, Strauss (2002) revealed that Salmonella
spp. may survive in biosolids over 100 days in lower moisture (10–15 C) and for
30 days in higher moisture (20–30 C), while fecal coliforms survived for over
30 and 8 days, respectively. Winfield and Groisman (2003) reported that Salmonella
spp. can survive for weeks in aquatic environments and for months in soils and
sediments.
There are two variables needed to quantify the risk from pathogens: (1) exposure
to a sufficient quantity of pathogens from inhalation or ingestion and (2) the dose of
pathogens must be in a sufficient quantity to overwhelm the immune system’s ability
to contain the pathogen (Epstein 2002).
Risk Assessment of Pathogenic Bacteria in Soil Fertilized

with Biosolids
The risk assessment of pathogenic bacteria in soil fertilized with biosolids aimed to
evaluate the presence of hazard in soil and to characterize the risks associated with
the hazard (Grohmann et al. 2003). In the 1970s, the authors have indicated that there
are no incidences of disease from land application of biosolids detected, but patho-
genic bacteria associated with biosolids present a potential problem (Pahren et al.
1979). Those conclusions were based on the fact that the biosolid-borne bacteria in
land application systems are poor competitors outside the host. However, these
reasons are theoretical reasons, the absence of critical techniques for determination
of pathogenic bacteria in the environment is the main reason to suppose the possi-
bility and not confirmations to presence a health risk associated with pathogenic
bacteria in soil fertilized with biosolids, since the researchers theorize that some
of pathogenic bacteria may enter a viable but non-culturable (VBNC) state under
the stress environment, these organism are not accurately measured by standard
culturing methods. Moreover, the explanation for why only some of pathogenic
bacteria have the potential to survive in the environment while others cannot needs
more studies. Risk assessment requires a clear methodological analysis (Huertasa
et al. 2008). Therefore, many of the technologies for the determination of
pathogenic bacteria in the environment have developed during the last decade.
These technologies contributed significantly to risk assessment associated with
pathogenic bacteria in soil.
Besides the survival of pathogenic bacteria in the soil is affected by temperature,

moisture, sunlight, the availability of organic matter, soil pH, soil particles, and the
presence of toxic substances, competitive organisms influence bacteria survival in
soils (Cools et al. 2001; Zhang et al. 2013; Ma et al. 2014). These factors signifi-
cantly influence the survival of bacteria. Naganandhini et al. (2015) investigated
persistence of Shiga-like toxin-producing E. coli (STEC) strains (O157-TNAU) and
nonpathogenic strain (MTCC433) in different soils of India. The study revealed that
the red laterite and tropical latosol enhanced E. coli O157-TNAU and MTCC
433 survival more than wetland and black cotton soils. In coco peat, E. coli O157
survived longer than E. coli MTCC 433. The analysis of data using double Weibull
model and the modeling parameters that were correlated with soil physicochemical
and biological properties using principal component analysis (PCA) revealed that
pH, microbial biomass carbon, dehydrogenase activity, and available N and P
contents of the soil improved E. coli strains in those soils and coco peat.
Conclusion
Many of the pathogenic bacteria are associated with the biosolids. Therefore, high
health risk is associated with the application of these biosolids in the agriculture.
More advanced technologies are required to minimize the risk associated with the
biosolids by reducing the concentration of the pathogens to less than detection limits.
Cross-References
Kitchen Wastewater
▶ Removal of Pharmaceutically Active Compounds from Contaminated Water and
Wastewater Using Biochar as Low-Cost Adsorbents, An Overview
▶ Treatment of Domestic Gray Water by Multicomponent Filters
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Monitoring and Risk Analysis of
PAHs in the Environment 39
Karishma Hussain, Raza R. Hoque, Srinivasan Balachandran,
Subhash Medhi, Mohammad Ghaznavi Idris, Mirzanur Rahman,
and Farhaz Liaquat Hussain
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 975
Polycyclic Aromatic Hydrocarbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 975
Molecular Structure and Physicochemical Properties of PAHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 977
Exposure to PAHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 978
Toxicity and Carcinogenicity of PAHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 979
Sources of PAHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 982
Distribution in the Environment (Air, Soil, Street Dust, Water, and Sediment) . . . . . . . . . . . . . . . 984
PAHs in the Atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 984
PAHs in Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 990
PAHs in Street Dust . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991
PAHs in Water and Sediment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 992
PAHs Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 993
K. Hussain (*)
Department of Bioengineering and Technology, Gauhati University, Guwahati, Assam, India
e-mail: karishma.hussain@gmail.com
R. R. Hoque
Department of Environmental Science, Tezpur University, Tezpur, Assam, India
e-mail: rrh@tezu.ernet.in
S. Balachandran
Department of Environmental Studies, Visva-BharatiSantiniketan, Santiniketan, West Bengal, India
e-mail: s.balachandran@visva-bharati.ac.in
S. Medhi · M. G. Idris
Department of Bioengineering and Technology (GUIST), Gauhati University, Guwahati, India
e-mail: subhashmedhi@gauhati.ac.in; mdghaznaviidris@gauhati.ac.in
M. Rahman
Department of Information Technology (GUIST), Gauhati University, Guwahati, India
e-mail: mr@gauhati.ac.in
F. L. Hussain
Research Scholar, Department of Chemistry, Dibrugarh University, Dibrugarh, Assam, India
e-mail: flhussain786@gmail.com

https://doi.org/10.1007/978-3-319-73645-7_29
974 K. Hussain et al.
Ecotoxic Effects of PAHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994

Toxicity Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994
Ecosystem Risk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 995
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 997
Abstract
Polycyclic aromatic hydrocarbons (PAHs) are a unique class of organic pollutants
containing two or more fused aromatic rings, which are toxic and potential
carcinogens. They are extensively studied compounds, and their occurrence has
been reported from various places over the world which indicates their ubiquitous
nature in our environment. Anthropogenic sources of PAHs are more dominant
than their natural source which include sources like combustion engines, resi-
dential heating, industrial activities, and biomass burning. USEPA has already
listed 16 PAHs [naphthalene, acenaphthylene, acenaphthene, fluorine, phenan-
threne, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)
fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene,
benzo(g,h,i)perylene, and indeno(1,2,3-c,d)pyrene] as most priority ones to be
analyzed in various environmental matrices. More so, benzo(a)pyrene is termed
as index or gold standard of the whole group of PAHs due to its high carcinogenic
potency. Once in the atmosphere, depending on their physical and chemical
properties, PAHs get distributed between gas, particle, and droplet phase. Aerial
movement is one of the major pathways for environmental distribution and trans-
boundary deposition of PAHs. Eventually, PAHs settle down in soils and street dust
and enter into aquatic environment. Soil and street dust act as direct sink of
atmospheric PAHs near to traffic and other combustion sources. From these envi-
ronmental compartments, rainwater and storm water easily wash away PAHs to
nearby aquatic bodies. Due to hydrophobic nature, PAHs in aquatic environment
are preferably partitioned and accumulate into the particulate phase of sediment.
PAHs, thus, occur in multicompartmental system of the environment and paved the
way for multiple routes of exposure to this class of carcinogen. Therefore, extensive
studies have been carried out for PAHs in different environmental matrices over the
world, and many places are revealed with very high exposure levels of PAHs.
Environmental PAHs have harmful effects on different types of organisms of
the ecosystem. PAHs attract considerable attention among researchers due to
continuous rise in death toll of human cancer worldwide. Toxic equivalency
factors (TEFs) were often employed to assess carcinogenic potential of individual
PAHs. Here, the maximum TEF of one is assigned to BaP, and other individual
PAHs are relative to BaP as BaP equivalents (BaPq). To characterize risk of PAHs
to surrounding organisms and ecosystems in aquatic environment, ecosystem risk
was often employed by researchers by using risk quotient (RQ) of individual
PAHs. Risk quotients (RQ) value indicated the levels of risk posed by certain
PAHs. Studies are revealed with high exposure risk in different environmental
matrices in several places around the world. However, only a few recommenda-
tions or guidelines exist worldwide for concentration of PAHs.
39 Monitoring and Risk Analysis of PAHs in the Environment 975
Keywords
Polycyclic aromatic hydrocarbon · Toxicity · Carcinogenicity · Ecotoxic Effects ·
Ecosystem risk
Introduction
Nowadays growth of large cities are associated with problems such as segregation,
neighborhood degradation, increased road traffic, socioeconomic deprivation, and
inequities in health, well-being, and health-care accessibility, which have become
central environmental as well as political issues in most countries (Irene et al. 2003).
The urban environment is strongly man-made and intermittently depreciated in
comparison to the characteristics of the natural environment where the respective
city developed (Loghin and Murtoreanu n.d.). Such typical urban developments at
the cost of environmental degradation lead to emergence of many environmental
issues including air, water, and soil pollution (Yang et al. 2010). The continuous
addition of motorization results in a sharp increase in the concentration of pollutants
in the urban air which subsequently adds to soil, street dust, water, and sediment
(Shuang et al. 2011). It is estimated that vehicular emission attributes about 40–80%
of the air quality crisis (Ghose et al. 2004). The direct consequence of all these
developments is degradation of environmental quality. This in turn affects not only
the individual but also the whole community in the big cities (Loghin and
Murtoreanu n.d.). Studies also reveal a close relationship of human health effect
with the actual level of exposure to pollutants (Wei and Chapman 2001).
Extensive research is already being performed in many such areas including
inorganic and organic pollutants in the environment with major developments in
case of organic pollutants in the last few decades (Gaga 2004).
Since industrialization, many organic chemicals that are naturally occurring
(e.g., petroleum) and synthetic are released into the environment from various
anthropogenic activities. The presence of more than 600 organic compounds have
already been reported in various matrices of the environment that belong to the
classes of petroleum hydrocarbons, polycyclic aromatic hydrocarbons, ketones,
aldehydes, volatile organohalogen compounds, monocarboxylic acids, pesticides,
alcohols, dicarboxylic amines, fatty acids, saccharides, and amino acids (Polkowska
et al. 2000). Petroleum or refined petroleum products are the largest source of
contamination in terrestrial, marine, and groundwater (Douglas and Uhler 1993).
Polycyclic Aromatic Hydrocarbon
The environmental contamination mainly by polycyclic aromatic hydrocarbons

(PAHs) is a major threat to human health (Skupinska et al. 2004). PAHs are
among the most notorious semivolatile organic pollutants and are considered as
hazardous air pollutants (HAP) in the group of the non-halogenated organic
compounds along with benzene, phenols, aldehydes, etc. (IARC 1983).PAHs are
ubiquitous in the environment, either as natural component (i.e., as products of
humus conversion by microorganism) or as pollutants (i.e., in dust emitted by
carbo- and petrochemical industry, in cigarette smoke, as a product of incomplete
combustion of organic materials, in particular during waste utilization and house
heating) (Bojakowska and Sokołowska 2001).
They are the class of compounds with two or more fused benzoid rings made up
of only carbon and hydrogen (Velasco et al. 2004) in linear, angular, or clustered
arrangements (Lundstedt 2003) (Fig. 1). Based on the molecular structure, PAHs are
commonly classified into two categories, namely, low-molecular-weight (LMW)
PAHs with four or fewer aromatic rings and high-molecular-weight (HMW) PAHs
with five or more rings. The United States Environmental Protection Agency
naphthalene acenaphthylene Acenaphthene Fluorene
Phenanthrene Fluoranthene Pyrene Anthracene
Benzo(a)anthracene Chrysene Benzo(b)fluoranthene
Benzo(k)fluoranthene Benzo(a)pyrene Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene Indeno(1,2,3-cd)pyrene
Fig. 1 Molecular structures of PAHs

(USEPA) has promulgated 16 unsubstituted PAHs as the most priority ones to be

analyzed in different environmental matrices (US EPA 1977). Among them, benzo
(a)anthracene (BaA), benzo(a)pyrene (BaP), benzo(b)fluoranthene (BbF), benzo(k)
fluoranthene (BkF), chrysene (Chry), dibenzo(a)anthracene (DBA), and indeno
(1,2,3-c,d)pyrene (IP) have been classified as possible or probable human carcino-
gens (US EPA 2002), and BaP is often chosen as a surrogate of the whole group of
PAH because of its recognition as being carcinogens (IARC 1987).
Their fate in the environment is controlled by their physicochemical properties,
especially nonpolarity and hydrophobicity triggering their persistence nature in
different environmental matrices (Srogi 2007). They are prone to bioaccumulation
and biomagnification coupled with long-range transport (Liu et al. 2017). Due to the
potential nature of carcinogenicity, mutability, and toxicity, PAHs have been listed
as contaminants that required monitoring (Liu et al. 2017; Balcioglu et al. 2014;
Wu et al. 2008). PAHs concentration levels have been set by the EU (Commission
E. 2013) (7), USEPA (US Environmental Protection Agency Regional Screening
Levels n.d.), the Netherlands (Ministry of Housing Spatial Planning and Environ-
ment 1994), and China (Ministry of Housing and Urban-Rural Development 2009).
Depending on volatility and molecular weight, PAHs can adsorb on soot surface
and can remain in the gas phase as well (Sánchez et al. 2013). Such particles then
appear in different environmental matrices such as ambient air, soil, street dust,
water, sediment, etc. and can be inhaled by human beings or consumed with food,
leading to major health problems, such as tumors, birth defects, and a variety of
pulmonary diseases (Kislov et al. 2013).
Molecular Structure and Physicochemical Properties of PAHs
In 1976, over 100 different PAHs found in the atmosphere were recognized, and in the
year 1981, in cigarette smoke, more than 200 PAHs were diagnosed (Lee et al. 1976,
1981). Many PAHs contain the same number of rings, but their differences in config-
uration lead to differences in the compound’s characteristics (Skupinska et al. 2004).
Molecular structure of 16 PAHs is shown in Fig. 1, and physical properties of the
16 PAHs are shown in Table 1. The typical features of PAHs are high melting and
boiling points (therefore they are solid), low vapor pressure, and very low aqueous
solubility (Masih et al. 2012). Vapour pressure and aqueous solubility of PAHs tend
to decrease with increasing molecular weight, on the contrary, PAHs are resistance to
oxidation and their reduction increases with increasing molecular weight (US EPA
2002). Thus, aqueous solubility of PAHs reduces for each additional ring (Masih
et al. 2010). PAHs dissolve effectively in organic solvent and are lipophilic in nature
which is measured by water-octanol partition coefficients (Kow). All PAHs are solid
having high melting and boiling points. Although PAHs are chemically inactive,
they easily bond to particulate matter. PAHs become highly thermo- and photosen-
sitive when adsorbed on dust surface and degraded at high temperature (50 C) as
well as on exposure to light especially ultraviolet and visible light (Zakrzewski
1995). Photooxidation is one of the principal pathways of PAH decomposition and
Table 1 Physical properties of 16 PAHs (Source: WHO 1998a)

Molecular Melting Boiling Vapor Solubility in
Compound weight point C point C pressure kPa water (mg/L)
Naphthalene 128.18 80.2 218 1.1 102 3.93
Acenaphthylene 152.20 92–93 265–280 3.9 103 3.93
Acenaphthene 154.20 90–96 278–279 2.1 103 1.93
Fluorene 166.23 116–118 293–295 8.7 105 1.68–1.98
Phenanthrene 178.24 96–101 339–340 2.3 105 1.2
Anthracene 178.24 216–219 340 36 106 0.076
Fluoranthene 202.26 107–111 375–393 6.5 107 0.2–2.6
Pyrene 202.26 150–156 360–404 3.1 106 0.077
Benzo(a) 228.30 157–167 435 1.5 108 0.01
anthracene
Chrysene 228.30 252–256 441–448 5.7 1010 0.0028
Benzo(b) 252.32 167–168 481 6.7 108 0.0012
fluoranthene
Benzo(k) 252.32 198–217 480–471 2.1 108 0.00076
fluoranthene
Benzo(a)pyrene 252.32 177–179 493–496 7.3 1010 0.0023
Dibenzo(a,h) 278.35 266–270 524 1.3 1011 0.0005
anthracene
Benzo(g,h,i) 276.34 275–278 525 1.3 1011 0.00026
perylene
Indeno(1,2,3- 276.34 162–163 530 Ca.1011 0.062
cd)pyrene
their secondary metabolite production in the atmosphere (Skupinska et al. 2004). In

the environment, substituted PAHs with functional groups such as –OH, -NO2, =O,
and –CH3 are also identified (Skupinska et al. 2004).
Exposure to PAHs
Human exposure to PAHs occurs through three possible ways which include respira-
tory tract, gastrointestinal tract, and skin contact. For a nonsmoking person, up to 70%
of PAH exposure can be associated with diet. The main sources of PAHs in diet
include cereals, oils, and vegetables. Cooked food (in particular food prepared over
open flame) is recognized as the major contributor of PAH intake in humans, for
example, in barbecued meat, the level of PAH can be as high as 10–20 μg/kg (Phillips
1999). Water is another very important source of PAHs. The highest acceptable
concentration of BaP in water is o.7 μg/L as recommended by WHO. It is estimated
that the mean intake of PAH with water is 1% of total acceptable level (WHO 1998a).
A primary factor of risk due to PAHs is smoking habit. It is estimated that having
smoked one cigarette can cause intake of 20–40 ng of BaP (Phillips 1996; O’Neill
1997). Considering the population density, the human exposure risk to atmospheric
PAHs is maximum in the cities (Caricchia et al. 1999). Although there is a shift in
the usage of coal toward other fossil fuel (oil or natural gas) for domestic heating
resulting into the drastic reduction of urban particulate pollution in cities, the
densification of the urban net coupled with increasing importance of traffic has
contributed to reinforce urban particulate pollution. Furthermore, particles generated
from cars are much smaller than coal particles and are mostly confined in the
breathable size fraction (Manoli et al. 2002). There is much information on the
HMW PAHs, but studies are comparatively very less for the vapor-phase LMW PAH
components. Although these LMW PAH compounds are considered to have weaker
carcinogenic/mutagenic properties, they are the most abundant in the urban atmo-
sphere and react with other pollutants to form more toxic derivatives (secondary
pollutant) (Park et al. 2002). Thus, it can be inferred that human exposure to mixtures
of PAHs, rather than to individual substances, is important.
Industrial workplaces such as coke plants; coal tar and pitch producing and
manufacturing industries; aluminum plants; iron and steel foundries; and creosote,
rubber, mineral oil, soot, and carbon black producing or manufacturing companies
are also associated with high exposure to PAHs. Such unusually high exposure to
PAHs was revealed after a significant increase in the incidence of certain cancer
diseases and was reported among the workers. Similarly, chimney sweeps, roadmen
(pavement tarring), and roofers (roof tarring) are under increased risk, included
among the highly exposed occupational groups (Jacob and Seidel 2002).
Toxicity and Carcinogenicity of PAHs
In the eighteenth century, higher rate of occurrence of skin cancer was reported
among roofers who were exposed to soot. Again in the year 1947, lung cancer was
found to be associated with working condition of gas industry workers and that of
coal tar (Kennaway 1995). It was then revealed that the induction of cancer was
caused by PAHs available in coal tar and soot (Kjaerheim 1999). In 1983, the
International Agency for Research on Cancer recognized 30 PAHs as carcinogenic
to people. PAHs attract considerable attention among researchers with the continu-
ous rise in death toll caused by cancer which account for about 13% of all human
deaths worldwide in 2007 (Jemal et al. 2011). Carcinogenic and mutagenic proper-
ties of a few PAH members have already been well established by researchers
(Grimmer 1983; Ramdahl and Bjorseth 1985; Dias 1987; U.S. EPA (Environmental
Protection Agency) 1993; Clement Associates 1990; Department of Health and
Human Services, Public Health Service, National Toxicology Program 2011;
U.S. Environmental Protection Agency n.d.; ATSDR (Agency for Toxic Substances
and Disease Registry) 1995; IARC (International Agency for Research on Cancer)
1996; IPCS/WHO (International Programme on Chemical Safety/World Health
Organization) 1998; Boström et al. 2002; Larsen and Larsen 1998; Bartoszek
2002; Baek et al. 1991a; Harvey 1998; Howsam and Jones 1998; NRC (National
Research Council) 1983) in experimental animals and humans. It is revealed from
studies on experimental animals that PAHs may trigger various health effects, such
as cytotoxicity, immunotoxicity, genotoxicity, carcinogenicity, reproductive toxicity,

etc. (IARC 1983). Carcinogenic classifications of selected PAHs put forward by
various agencies are given in Table 2.
All PAHs do not show the same toxicity depending upon the structure of a particle
and substituted groups of PAHs. Many PAHs belong to the group of carcinogens such
as unsubstituted PAHs, the PAHs containing nitrate, methyl, and carboxylic group
(Skupinska et al. 2004). Benzo(a)pyrene (BaP) is termed as index or “gold standard” of
the whole group of PAHs due to its high carcinogenic potency (U.S. EPA (Environ-
mental Protection Agency) 1993, n.d.). Carcinogenicity of BaP through inhalation was
tested only in hamsters (Thyssen et al. 1981; WHO 2000). Risk analysis inferred that
about 9 per 100,000 individual spending a lifetime in ambient air exposed to average
level of BaP of 1 ng/m3 may die from respiratory tract cancer (Larsen and Larsen 1998;
WHO 2000). Car exhausts (petrol, diesel), domestic coal-stove emissions, and tobacco
smoke releasing mainly four- to seven-ring PAHs are found to exhibit nearly all the
carcinogenic potential (Pott and Heinrich 1990). Elevated levels of DNA adduct,
mutations, reproductive effects, and cancers of lung, respiratory tract, and urinary
bladder are found to be associated with exposure of PAHs (Bosetti et al. 2007; Gaspari
et al. 2003). According to Pankow et al. (Pankow et al. 1993), carcinogenic risk of
inhaled PAHs depends upon whether it enters into lung in gas form or particulate; in
case of particulate, PAH carcinogenicity prevails for longer period of time.
Mutagenic activities of 67 PAHs were studied in human lymphoblastoid
by Durant (Durant 1996) in which human lymphoblastoids were grown in the
presence of different concentrations of the studied PAHs. According to the study,
the mutagenic activities of PAHs are found to be as follows: dibenzo(a,l)pyrene
> benzo(a)pyrene > indeno(1,2,3-c,d)pyrene > dibenzo(a,h)anthracene > benxo(b)
fluoranthene > benzo(g,h,i)perylene > antraquinone >9-nitroanthracene > ben(e)
pyrene phenanthrene and pyrene. In case of benzo(a)pyrene and dibenzo(a,l)
pyrene, it was revealed that the change in the number of rings results into difference
in toxicity of those PAHs. It was also observed that PAH’s biological activities were
not only controlled by the number of rings but also the shape, the dimension of
particles, and the presence of functional groups. In the studies, it was observed that
some PAHs are even stronger carcinogens than BaP. Nevertheless, BaP is still used
as an indicator of whole group of PAHs (Phillips 1999).
It is critical to establish the levels of PAHs that are safe for humans. The highest
acceptable levels of PAH concentrations in various countries are presented in Table 3
(Kjaerheim 1999; Khesina 1994; Slooff et al. 1989; WHO 1998b; European eco-
nomic community 1980; Disposition of German Federal Department for worker
safety 1989; Disposition of Swedish National Board of Occupational Safety and
Health 1994; American Conference of Governmental Industrial Hygienists 1995). In
Poland since 2001, the maximum acceptable level in a workplace has been set to be
2 μg/m3 (Corpus of Polish Law (Dziennik Ustaw) 2001). According to the Ministry
of Environment in Great Britain Ascertained in the Air Quality norm, it is not
possible to estimate the absolutely safe level of exposure to carcinogens
(in particular PAH) (UK Department for Environment, Food, and Rural Affairs
1999). In reality, there is no such idea as safe concentration for carcinogenic and
Table 2 Carcinogenic classifications of PAHs by various agencies

Agency PAH compounds Carcinogenic classification
US Department of Health and Benzo(a)anthracene Known animal carcinogens
Human Services (HHS) Benzo(b)
fluoranthene
Benzo(a)pyrene
Dibenzo(a,h)
anthracene
Indeno(1,2,3-cd)
pyrene
International Agency for Research Benzo(a)anthracene Probably carcinogenic to humans
on Cancer (IARC) Benzo(a)pyrene
Benzo(a) Possibly carcinogenic to humans
fluoranthene
Benzo(k)
fluoranthene
Indeno(1,2,3-cd)
pyrene
Anthracene Not classifiable as to their
Benzo(g,h,i) carcinogenicity to humans
perylene
Benzo(e)pyrene
Chrysene
Fluoranthene
Fluorene
Phenanthrene
Pyrene
US Environmental Protection Benzo(a)anthracene Probable human carcinogens
Agency (EPA) Benzo(a)pyrene Not classifiable as to their
Benzo(b) carcinogenicity to humans
fluoranthene
Benzo(k)
fluoranthene
Chrysene
Dibenzo(a,h)
anthracene
Indeno(1,2,3-cd)
pyrene
Acenaphthylene
Anthracene
Benzo(g,h,i)
perylene
Fluoranthene
Fluorene
Phenanthrene and
Pyrene
Table 3 Maximal permissible concentrations (MPC) of PAHs in selected countries

Country year Occurrence Compound MPC
Italy 1999 Ambient Benzo(a)pyrene 1 ng/m3 (Kjaerheim 1999)
air
Former USSR Ambient Benzo(a)pyrene 1 ng/m3 (Khesina 1994)
1985 air
EEC 1980 Ambient Sum of 1.2 μg/l (Slooff et al. 1989)
water fluoranthene,
Benzo(b)
fluoranthene,
Benzo(k)
fluoranthene,
Benzo(a)pyrene,
Benzo(g,h,i)
perylene,
Indeno(1,2,3-c,
d)pyrene
WHO 1995 Drinking Benzo(a)pyrene 0.7 μg/l (WHO 1998b)
water
EEC 1980 Drinking Sum of 0.2 μg/l (European economic community
water fluoranthene, 1980)
Benzo(b)
fluoranthene,
Benzo(k)
fluoranthene,
Benzo(a)pyrene,
Benzo(g,h,i)
perylene,
Indeno(1,2,3-c,
d)pyrene
Germany 1989 Oven area Benzo(a)pyrene 2 μg/m3 (Disposition of German Federal
Department for worker safety 1989)
Sweden 1993 Workplaces Benzo(a)pyrene 2 μg/m3 (Disposition of Swedish National
Board of Occupational Safety and Health
1994)
USA 1993 Workplaces Pyrene 0.1 mg/m3 (American Conference of
Governmental Industrial Hygienists 1995)
mutagenic substances. For such substance, even a very small amount can increase
the risk of neoplastic diseases by accumulating continuously for years after entering
the living organism (Skupinska et al. 2004).
Sources of PAHs
Generation of PAHs is associated with incomplete combustion of materials

containing carbon and hydrogen such as coal fuel, crude oil, wood, gas, and organic
materials as well as combustion of polypropylene and polystyrene, communal and
industrial waste, and used tires (Cherng 1996; Lewitas et al. 1997). The process of
combustion is considered to be incomplete when the temperature of combustion is low
and atmosphere is anaerobic. Free radicals initiate the chemical synthesis of hydro-
carbon in the flame. Typically, free radicals of high molecular weight lead to the
production of large particles of PAHs although methane can also give on to generation
of PAHs particles. The aromatic compounds and diolefins can be precursors of PAHs
(Skupinska et al. 2004). Although some PAHs in the environment are released from
natural sources of combustion such as forest fires and volcanoes along with some
minor biogenic sources, emissions from anthropogenic activities predominate (Baek
et al. 1991a; Harvey 1998; Finalyson-Pitts and Pitts 1986). Anthropogenic sources of
PAHs can be broadly classified into stationary and mobile sources. Stationary sources
of PAHs include residential heating, industrial activities (e.g., aluminum production
and coke manufacture), incineration, and power generation. Diesel and gasoline
engine vehicular exhaust are categorized as mobile sources of PAHs (Gaga 2004).
In general, stationary fuel sources are considered to be responsible for over 97% of
PAH emissions (Pikes 1992). However, the profile is different in case of an urban area
with high traffic density (Gaga 2004). According to Shen et al. (2013), global total
atmospheric emission of USEPA-listed 16 priority PAHs was 504 Gg in 2007 with
maximum contribution of about 60.5% from biomass fuels combustion, mainly
firewood and crop (Samburova et al. 2017). Some of the examples of natural sources
of PAHs are forest and brush fires, volcanoes, bacterial and algal synthesis, petroleum
seeps, erosion of sedimentary rocks containing petroleum hydrocarbons, and decom-
position of vegetative liter fall (Zhang and Tao 2009).
Anthropogenic sources of PAHs can also be categorized as petrogenic and
pyrogenic. Pyrogenic PAHs resulted from incomplete combustion of any organic
material, while the petrogenic PAHs are found in oil and some of its product (Feng
et al. 2009; Lang et al. 1962, 1964). In general, the pyrogenic PAHs are comprised of
larger ring than the petrogenic PAHs (Pampanin and Sydnes 2013).
Pyrogenic PAHs are formed by the process of pyrolysis (transformation
of organic substances under high temperatures and low oxygen or no
oxygen conditions) such as destructive distillation of coal into coke and coal tar or
the thermal cracking of petroleum residuals into lighter hydrocarbons
that occur intentionally. On the other hand, other unintentionally occur pro-
cesses include the incomplete combustion of motor fuels in cars and trucks, the
incomplete combustion of wood in forest fires and fireplaces, and the incomplete
combustion of fuel oils in heating systems. The pyrogenic processes occur in
the temperature ranging from about 350 C to more than 1200 C. Higher concen-
trations of pyrogenic PAHs are typically found in urban areas mainly close to major
sources of PAHs. Moreover, PAHs can also be generated at lower temperatures.
PAHs are produced during crude oil maturation, and similar processes are termed as
petrogenic. Such petrogenic PAHs are released during transportation, storage, and
use of crude oil and crude oil product such as oceanic and freshwater oil spills,
underground and aboveground storage tank leaks, and the accumulation of vast
numbers of small releases of gasoline, motor oil, and related substances associated
with transportation (Tolosa and Bayona 1996; WHO (World Health Organization)
2003; Masih and Taneja 2006; Seo et al. 2007).
There are numerous and well-known sources of PAHs in the environment

depending upon the prevailing activities, atmospheric conditions, and topography
of the area. Analysis of real environment samples helps in the identification of the
PAHs. Differentiation between groups of PAH sources (coal-based, wood-based, or
oil-based sources) is performed by chemical fingerprinting with several techniques.
This can be performed by studying the behavior of different chemical indicators that
exist in the environmental samples. This source identification technique can also be
used to identify and assign nonpoint sources of PAHs to the environment irrespective
of their land-use pattern (Wang et al. 2011a). Temperature of formation impart one
fundamental information in identifying PAH sources due to the fact that higher
temperature of formation tend to generate PAHs with fewer alkylated chains than
that under lower temperature (Hussein et al. 2016).
PAH dispersion is regulated by thermodynamic properties during low-temperature
processes and by kinetic characteristics during high-temperature processes, such as
pyrolysis of organic matter (Alberty and Reif 1988). As for example, phenanthrene is
thermochemically more stable than anthracene; molar fraction of phenanthrene
produced is much higher than that of anthracene at low temperature. On the other
hand, high-temperature combustion such as incomplete burning of organic matter is
characterized by low value of phenanthrene/anthracene ratio (Baumard et al. 1998).
Distribution in the Environment (Air, Soil, Street Dust, Water,

and Sediment)
PAHs are well-dispersed environmental pollutant arising from anthropogenic sources

(Baek et al. 1991a; Nollet 2007; Petry et al. 1994, 1996). Aerial movement is one of
the crucial pathways for environmental distribution and transboundary deposition of
PAHs (Birgül et al. 2011). Due to their long-range transport, remote areas far from
emission sources also get exposed to PAHs (Montelay-Massei et al. 2007a; World
Health Organization 2002). Eventually, PAHs settle down in soils and street dust and
enter into aquatic ecosystem (Christensen and Arora 2007; Tolosa et al. 2004). Soil
and street dust behave as direct sink of atmospheric PAHs near to combustion sources
such as traffic. Rainwater and storm water washed away PAHs from these environ-
mental compartments to nearby aquatic bodies. Due to hydrophobic nature, PAHs in
aquatic environment are preferably partitioned and accumulate into the particulate
phase of sediment (Gaga 2004). PAHs, thus, occur in multicompartmental system of
the environment (Holoubek et al. 2000; Finlayson-Pitts and Pitts 2000) and paved the
way for multiple routes of exposure to this class of carcinogen. Figure 2 illustrates
distribution of PAHs in various environmental matrices.
PAHs in the Atmosphere
It is fully established that atmospheric transfer is the principal pathways for the
global distribution of PAHs (Birgül et al. 2011). Once in the atmosphere, depending
Fig. 2 PAHs distribution via air, terrestrial and aquatic environment
on their physical and chemical properties (vapor pressure, Henry’s law constant, and
solubility), PAHs get distributed between gas, particle, and droplet phase (Junge
1977; Bidleman 1988; Larsen III and Baker 2003; Gocht et al. 2007). Most of the
studies revealed that the two- and three-ring PAHs are mainly found in the vapor
phase, while four- to six-ring PAHs occur in the particle phase at ambient temper-
ature, (Zhang et al. 2009; Teixeira et al. 2013; Delgado-Saborit et al. 2013; Alam
et al. 2013). PAH’s wash out mechanism from atmosphere occurs through two major
pathways: oxidative and photolytic reactions and atmospheric fallouts (Garban et al.
2002; Manoli et al. 2000). Atmospheric bulk (dry+wet) deposition is another
mechanism associated with the removal of vapor as well as particle-bound PAHs
in the air according to Bidleman et al. (Bidleman 1988). Particle-phase concentration
and meteorological factors play a very crucial role in deposition of PAHs (Liu et al.
n.d.). Extensive studies have been carried out to explore relationship between
meteorological parameters and PAH concentrations. Remarkable relationship of
PAHs with temperature and relative humidity were documented by Pankow et al.
(1993) and Chetwittayachan et al. (2002). It was also observed that temperature
variation has more impact on gas-phase LMW PAH dispersion than particulate-
phase HMW PAHs (Sofuoglu et al. 2001).
In most of the studies, PAH concentrations were observed with minimal value
during summertime or monsoon than that of winter, due to the fact that there is
increase in the mean inversion height, decrease in the number of inversion days
during winter, and lack of a major PAH source and residential fuel combustion for
heating (Baek et al. 1991b; Hussain et al. 2016a). Another observation also revealed
that maximum concentration of particle-associated PAH was found during winter,

while vapor-phase PAHs were maximum during summer (Baek et al. 1991b).
Considering the risk of human exposure to atmospheric PAHs, it was revealed
from studies that exposure risk to atmospheric PAHs is highest in cities due to
increasing density of population, vehicular traffic, and insufficient dispersion of the
atmospheric pollutants (Rockens et al. 2000). The prescribed or mandatory concen-
tration level of BaP is 1 or 10 ng/m3 air in various countries (e.g., Italy or Germany)
(Jacob and Seidel 2002).
Gas to Particle Distribution of PAHs in the Atmosphere

PAHs exist in both vapor and particulate phase [mainly the fine fraction (<1 μm)] in
the atmosphere owing to their semivolatile property (Aceves and Grimalt 1993; Allen
et al. 1996). The fate and deposition of PAHs in the environment are critically
regulated by this phase partitioning. Gaseous exchange at various surfaces such as
sea, vegetation, soil, etc. is another important mechanism of PAHs during their
dispersion in various matrices of the environment (Dickhut and Gustafson 1995;
McLachlan 1999; Sweetman et al. 2005). Understanding gas/particle partitioning of
these semivolatile organic pollutants both in rural and urban atmosphere allows us to
reveal various aspects such as their partition and subsequent influence on health effect
(Pankow et al. 1993), their removal by dry and wet deposition from an air shed
(Pankow et al. 1984; Ligocki et al. 1985a, b; Leuenberger et al. n.d.; Tsai et al. 1991),
their formation of secondary pollutants by photolysis (Kamens et al. 1989) (WHO
(World Health Organization) 2003), and their removal by advection (Tsai et al. 1991).
Gas/particle partition of PAHs is controlled by various factors such as the
molecular weight of the compounds, temperature, humidity, and precipitation (Sub-
ramanyam et al. 1994; Van Jaarsveld et al. 1997). Typically, low-volatile PAHs with
>5 rings are exposed to relatively high-temperature condensation and are mostly
adsorbed to atmospheric particles (Van Jaarsveld et al. 1997; Wania and Mackay
1996). These PAHs are often subjected to rapid deposition and retention close to the
source and are therefore listed as “single-hop” persistent organic pollutants (POPs)
due to their low mobility (Wania and Mackay 1996; Yang et al. 1991; Agarwal
2009). On the contrary, the LMW PAHs with two to three rings undergo
low-temperature condensation and found mostly in the gas phase (Subramanyam
et al. 1994; Van Jaarsveld et al. 1997; Wania and Mackay 1996; Valerio et al. 1984;
Wild and Jones 1995). This category of PAHs is termed as “multi-hop” chemicals
due to their high or moderately high mobility (Wania and Mackay 1996). As a result,
LMW PAHs diffuse in the air worldwide and preferentially cumulate in polar
latitudes (Van Jaarsveld et al. 1997; Wania and Mackay 1996). Semivolatile (four-
ring) PAHs can exist both in particle and gas phase and are mostly induced by
environmental factors (Subramanyam et al. 1994). They get preferably settled and
enriched in midlatitudes (Wania and Mackay 1996).
Thus, individual PAH depending upon their molecular weight and structure func-
tions differentially under different meteorological and climatic conditions. Meteoro-
logical parameters (temperature and relative humidity) play a crucial role in diffusion
of LMW PAHs (Pankow et al. 1993; Zielinska et al. 2004). Vapor pressure influencing
volatilization has been found to be governed by temperature, humidity, and wind

speed. With the increase of temperature, PAH volatilization from air particles, soil,
vegetation, and water also increases (Sofuoglu et al. 2001; Ausma et al. 2001). There is
also a report of rise in absorption of semivolatile organic compounds as relative
humidity approaches 100% (Thibodeaux et al. 1991). Such increment at very high
relative humidity is associated with partitioning into the liquid or nearly liquid water
when the gas phase is nearly saturated with water (Thibodeaux et al. 1991).
Significant correlation between vapor pressure and molecular weight with a
correlation coefficient of 0.9017 was also reported (Schwarzenbach et al. 1993).
As for example, PAHs with lower vapor pressures such as BaP will prefer to be bind
to particles, while PAHs with higher vapor pressures such as naphthalene will tend to
be sorbent with the vapor phase. Thus, for atmospheric samples, the relative
dispersion of PAHs in the two phases will be distinct. According to the atmospheric
study in Portland, Oregon, conducted by “Electric Power Research Institute (EPRI)”
(EPRI (Electric Power Research Institute) 2000), the sum of PAH concentration for
the vapor phase (741 ng/m3) was much higher than that of the particulate phase
(12 ng/m3). Moreover, it was also revealed in the study that the majority of
LMW/higher vapor pressure PAHs were identified in the vapor phase, whereas the
HMW/lower vapor pressure PAHs were detected with much lower concentrations
(EPRI (Electric Power Research Institute) 2000). The amounts of dust in the air and
PAH concentrations in the particulate phase were also found to exhibit significant
correlation (Kuo et al. 2013). As a result of which, the levels of gas-phase PAHs are
dominant in summer or typically in tropical regions, whereas particulate-phase PAHs
are found to be prevalent during winter or typically in Arctic regions (Lai et al. 2011;
Mohanraj et al. 2012). Furthermore, types of suspended particulates such as soot,
dust, fly ash, pyrogenic metal oxides, pollens, etc. also influence PAH adsorption
(Zhang and Tao 2009).
Air Water Gas Exchange of PAHs

Air-water transfer processes for PAHs include volatilization and absorption of gases,
dry deposition with particles, and wet deposition by rain or snow, i.e., particle and gas
“washout,” spray transfer, and bubble scavenging (Gustafson and Dickhut 1997).
Air-water transfer is regulated by Henry’s law, according to which PAH concen-
tration in water is proportional to the partial pressure of PAHs in air:
pa ¼ H a X w
where pa is the partial pressure in air, Ha is Henry’s constant (both in pressure units),
and Xw is the mole fraction in water. The lower is the Henry’s constant, it is more
preferable that PAHs will partition from air to water (Fisher 2001).
Atmospheric Pollutant Removal Processes

Anthropogenic activities are basically liable for release of chemical pollutants
into the environment. If all the pollutants persist in various environmental compart-
ments as it is, their ambient levels should equal to the aggregate amounts
discharged. However, typically this is not the case, as each environmental matrix in
nature has some active naturally occurring removal or “self-purification” processes
(Schlesinger 1979).
Gas- and particle-associated PAHs in air are subjected to removal mechanism
such as oxidative and photolytic reactions and ultimately from the atmosphere by
two mechanisms, namely, wet and dry deposition (Garban et al. 2002).
Removal of pollutants from the atmosphere in the absence of precipitations
onto various surfaces of earth is termed as dry deposition. Whereas, the scaveng-
ing processes by which pollutants are encapsulated by hydrometeors and conse-
quently dropped to the Earth’s surface is referred as wet deposition (Seinfeld and
Pandis 1998).
Thus, the released airborne PAHs are moved by the prevailing meteorology
before being washed from the atmosphere by different scavenging processes. Wet
deposition (rain, sleet, snow, hail) and dry deposition are considered as the major
mechanisms of removal of PAHs from the atmosphere. Studies revealed that the
wet removal pathway of gaseous PAHs was better understood than particulate
PAHs (Ligocki et al. 1985a). The scavenging mechanism, such as in-cloud or
below-cloud, collection efficiency of falling precipitation, solubility, and size
particles have been well investigated in literature (McVeety 1986; Sharma and
Patil 1994).
Nonreactive gaseous organic compounds are washed out by rain between the
gas and aqueous phases according to the Henry’s law equilibrium (Ligocki et al.
1985a, b). According to Pankow et al. (1984), the total degree of scavenging of a
given compound when there is no exchange of material between the particulate and
dissolved phases in the rain can be expressed as follows:
W ¼ W g ð1 ϕÞ þ W p ϕ
where W is the overall scavenging ratio:
W ¼ ½rain, total =½air, total
Wg is the gas scavenging ratio:
W g ¼ ½rain, dissolved =½air, gas
Wp is the particle scavenging ratio:
W p ¼ ½rain, particulate =½air, particulate
and ϕ is the fraction of the atmospheric concentration which is associated with

particles. For compounds which (1) are scavenged to some degree from the atmo-
spheric particulate phase and (2) remain on particulate material inside the raindrop,
W will differ from the equilibrium Wp value. The second state become necessary as
material which is moved to the dissolved phase will undergo rapid re-equilibration
with the atmosphere.
Fig. 3 Sources, transport, and deposition of PAHs via the atmosphere
Dry deposition is a function of prevailing atmospheric state and the concentration

of PAHs in surface level. PAHs adsorbed particle size greater than 20 μm are
vulnerable to settle near the source due to their high-settling velocity. However,
this PAH removal mechanism occurs only to minor percentage as PAH is predom-
inantly adsorbed on particle diameter of <10 μm (Thornton et al. 2001).
An illustration of sources, transport, and deposition of pollutants via the atmo-
sphere is shown in Fig. 3.
Atmospheric Bulk Deposition of PAHs

Typically, the atmospheric deposition can be categorized into wet and dry deposition
(Leister and Baker 1994; Buehler et al. 1998; Brun et al. 2004). The entire flux for
both the mechanisms is controlled by processes including scavenging of vapor and
particles, particle sedimentation, and surface-gas absorption. It is needed to evaluate
both dry and wet deposition to determine the total atmospheric deposition of PAHs
(Golomb et al. 2001). Bulk samplers account the grand total of all the atmospheric
removal processes as they do not differentiate between the two (Gocht et al. 2007).
The atmospheric bulk deposition of individual PAHs is induced by the various
parameters, namely, the compound’s Henry’s law constant and vapor pressure, the
particle size distribution, the gas/particle partitioning, meteorological conditions,
and the size of raindrops (Manoli et al. 2000; Sehmel 1973). Thus, physical and
chemical properties as well as climatic conditions regulate the diffusion of PAHs in
the environment (Montelay-Massei et al. 2003).
Generally, dry air PAHs that do not get transported far from emission sources have
short life of few to 10 h (Golomb et al. 2001; Montelay-Massei et al. 2003), whereas
the aqueous-phase PAHs have a lifetime of approximately 10–100 h (Mackay et al.
1992). In-cloud and below-cloud scavenging of PAHs associated with gas and
particulate phase travel over long distances. Thus dry deposition preponderates in
urban/industrial areas while wet deposition in remote areas in general (Golomb et al.
1997). Hence, in order to record atmospheric deposition loadings, it appears inevita-
ble to include both dry and wet depositions (Garban et al. 2002).
During the past few decades, PAH in bulk deposition (dry + wet) has been widely
studied (Garban et al. 2002; Manoli et al. 2000; Hussain et al. 2016a; Ollivon et al.
2002; Grynkiewicz et al. 2002; Montelay-Massei et al. 2007b; Delhomme et al.
2007; Esen et al. 2008; Wang et al. 2011b).
PAHs in Soil
Air to surface precipitation by dry or wet deposition is considered to be the key

pathway for PAHs input into soil surface (Wang et al. 2002; Tao et al. 2003). Soil is,
therefore, one of the major sinks of atmospheric PAHs (Morillo et al. 2008). Besides,
volatilization, irreversible sorption, leaching, accumulation by plants, and biodegra-
dation are the viable mechanisms for dispersion of PAHs (Reilley et al. 1996).
Surface runoff and dust re-suspension from soil can also act as a source of air and
sediment contamination (Mai et al. 2003). Study also revealed significant relation-
ship of PAH concentration in soil well with their representative levels in air (Vogt
et al. 1987), house dust (Chuang et al. 1995), and urban street dust (Takada et al.
1990; Essumang 2006). Soil therefore can be used as a good index for PAH pollution
and environmental risk (Liang et al. 2011).
Soil acts as a crucial sink for the combustion products that are released into
the atmosphere. Soil is, therefore, considered as the major channel for buildup as
well as assimilation of many pollutants (Wild and Jones 1995). Soil contamination
with PAHs is an emerging problem predominantly in urban areas with growing
energy consumption (Dai et al. 2008). Such increase over time mark the intensifi-
cation of emission rate associated with typically industrialization, urbanization, and
motor vehicles.
Motor vehicle emissions are mainly contributed by a mix of tailpipe emissions,
wear and tear of brakes and tires, and re-suspension of street dust (Rogge et al. 1993;
Thorpe and Harrison 2008). Much of the combustion-associated PAHs are found to
be available on the top layer of the soil (Agarwal 2009). Moreover, human exposure
of PAHs via soil has been reported to be more pronounced than that of air and water
(Menzie et al. 1992). Smith et al. (1995) reported significantly high PAHs burden in
soil ( 95%) in contrast to that in air ( 0.2%).
Thus, PAHs either from nearby sources, e.g., automotive exhausts from adjacent
roadways, or from more distant sources, e.g., industries, have been transported to
various distances through the air. Over the course of time, PAHs can be built up to
soils if fill materials carry PAHs. PAHs can become mobile after they get deposited on
the earth’s surface. The vital aspect determining PAH mobility of particulates in the
subsurface include sorbent particle size and the pore throat size of the soils (Hussein
et al. 2016) as most of the PAHs in the soil will be bound to soil particles (Masih and
Taneja 2006; Cachada et al. 2012). Such pore throat can be described as the smallest
opening found between individual grains of soil (Riccardi 2013). Movement of PAHs
will be restricted if PAH-bound particles cannot move through the soil, and they will
be likely to remain sorbet to particles. Individual properties of the PAH and the soil
are the determining factor for the affinity of PAHs to be sorbet to soil. Hence, PAH
sorption is one of the mechanisms that direct the soil mobility of individual PAH. The
octanol-water partitioning coefficient of PAHs is another vital factor influencing the
sorption of PAHs to soils. The octanol-water partitioning coefficient (Kow) is linked to
the solubility of an organic compound in water (Schwarzenbach et al. 1993). With the
increase of Kow, the aqueous solubility decreases and the affinity for sorption to a
particular soil increases. Yet, the Kow and solubility can influence PAH mobility in
soil. Other factors, for instance, soil conductivity, also have a considerable control on
PAH movement (Shang et al. 2014).
Hydrophobic nature and stable chemical structure of PAHs which favor adsorp-
tion onto soil particles paved the way for sustaining capacity of PAHs in soil matrix
for longer time (Means et al. 1980; Wilcke et al. 2000). PAHs are therefore termed as
persistent and poorly degraded contaminants of the soil. Significant correlation of
PAH concentration with soil organic carbon (OC) content is reported in literature
(Liang et al. 2011). Such association of PAHs with soil organic matter could make
PAHs become more resistant to degradation (with the increase of organic matter
content) (Man et al. 2013).
In some studies, black carbon (BC) is found to play a crucial role in the
distribution of PAHs in the soil due to their co-emission and high sorption capacity
for PAHs (Agarwal and Bucheli 2011; Liu et al. 2011; Hussain and Hoque 2015). BC
is also acknowledged as strong adsorbent for hydrophobic organic compounds. This
adsorption also diminishes toxicity and biodegradability of organic contaminants in
the soil (Semple et al. 2013). Thus, the fate and behavior of contaminants are the
primary aspects during their risk estimation and remediation (Riding et al. 2013).
PAHs in Street Dust
Street dust is chemically most alike to the primary portion of atmospheric aerosol
and reveals a critical relationship through continuous process of resuspension into
and redeposition from atmosphere (Wang et al. 2002). Rapid urbanization triggering
transport of increasing population and goods by large number of motor vehicles has
given rise to escalating levels of pollution along roadways (Loganathan et al. 2013).
Thus, levels of PAHs in street dust are determined by the key factors like traffic
density and rate of deposition in street dust (Edwards 1983; Jones et al. 1989;
Novotny and Olem 1993).
Street dust is often reported as the direct sink of deposited PAHs near to sources
mainly from traffic. It is very much rational that closer to the highway faster
deposition of exhaust aerosol droplets takes place, while going away dust particles
that are dispersed with wind disrupt their adsorption (Tuhackova et al. 2001) and
afterward affect other environmental matrices (e.g., air, water, soil, and plants)
(Samimi et al. 2009). This consecutively raises significant exposure risk for human
population (Hassanien and Abdel-Latif 2008) mainly for those who live by the
roadside. Although anthropogenic and biogenic sources of PAHs contribute to street
dust load by atmospheric deposition process (Yang and Chiang 1999), part of street
dust PAHs may move to atmosphere through the means of evaporation and wind
raise (Aryal et al. 2005). Rainwater easily washed out PAHs from street dust to
drainage and subsequently to nearby water bodies such as river, estuaries, etc.
(Hofmann et al. 1984; Hidlemann et al. 1991). PAH contribution from dry deposition
to street dust was observed to be more than 95% (Yang and Chiang 1999), and motor
vehicles account for a noteworthy aid to total PAHs load in street dust.
Multiple sources of PAHs in urban street dust consist of weathered materials
of road surfaces, automobile exhaust, lubricating oils, gasoline, diesel fuel, tire
particles, construction materials, and atmospherically deposited materials
(Murakami et al. 2005).
PAHs in Water and Sediment
Surface water and sediment delineate vital enlightenment regarding anthropogenic

activities neighboring to a water body. Typical pathways of PAHs inflowing to
aquatic environments comprise of direct wet or dry deposition from atmosphere,
runoff from land, roads, pavements, roofs, guttering and industries (Marsalek et al.
1999; Van Metre et al. 2000), and direct water outlet (Maliszewaska-Kordybach
1999). It has been estimated that atmospheric sources contribute 10–80% of PAH
inputs to the world’s oceans (Manoli and Samara 1999). Predominantly, anthro-
pogenic sources of PAHs in aquatic environment can be both pyrogenic and
petrogenic. Pyrogenic sources of PAHs are combustion of organic matter like
petroleum fuel, coal, and biomass. Petrogenic PAHs (from crude and refined
petroleum products) can go into aquatic environments via accidental oil spills,
oil spills from tanker-used engine oils, natural seeps, offshore drilling, urban
runoff, creosoted pilings municipality and urban runoff, and industrial processes
(Singare 2015). Occurrence of higher levels of PAHs in urban runoff was reported
during autumn and winter owing to the high frequency of vehicles plying in the
streets as well as the increased use of heating systems (Manoli and Samara 1999).
Storm water is an utmost distribution route of PAHs to the receiving water bodies
regardless of types of sources of PAHs in urban areas. Hence, to tackle fruitful
control and remediation of these pollutants, their source and sink have to compre-
hend well (O’Reilly et al. 2010).
Upon entering aquatic systems, PAHs are diffused by currents and sooner or
later become integrated with the sediment (EPRI (Electric Power Research Insti-
tute) 2000; Tehrani et al. 2012). There, PAHs ideally tend to settle, partition, or
adsorb onto nonaqueous phase such as soil or sediment owing to their
hydrophobicity (Cornelissen et al. 2006) and high octanol/water partition coeffi-

cients. This trace has been employed by several investigators by exploring the
depositional history in sediment cores to recognize trends of PAH contribution into
the environment. These cores are typically occupied in anoxic sediment, where
there is no oxygen in the water (EPRI (Electric Power Research Institute) 2000;
Tehrani et al. 2012).
PAHs become less susceptible to degradation after they get adsorb to solid
particles (Guzzella and Depaolis 1994). Yet, PAHs are not entirely insoluble, chiefly
the LMW PAHs. Accordingly, small amounts of PAHs dissolve and incorporated in
the pore water where they are bioavailable. Moreover, the existence of pore water
organic colloids render raise in the levels of PAHs beyond their aqueous solubility
since PAHs will be sorbet onto these organic colloids. Sequentially, they are trans-
ferred through the pore spaces of the sediment effortlessly. As a result, the mobility
and bioavailability of PAHs in sediments intensify with the sorption of PAHs to
colloids (Dong et al. 2012).
Mutagenic and carcinogenic effects of PAHs to land and water organisms (Connel
et al. 1997), study of their distribution, and source identification of PAHs in aquatic
environment near urban centers have attained much attention over the world. High
toxicity and high stability in the environment and lipophilic characteristics of PAHs
facilitate them to carry through food chains with human being as final recipient
(IARC 1983; Okay et al. 2000; Vagi et al. 2005). The EU Directive 98/83/EC,
relevant to drinking water, has prescribed limit of 0.10 μgl1 for the sum concen-
tration of BbF, BkF, BgP, and IP and 0.010 μgl1 for BaP (European Communities
(Drinking Water) Regulations 2007).
According to the study of WHO in 1997, the levels of individual PAHs in surface
and coastal waters are by and large in the vicinity of 0.05 lg/L, and the concentration
above this point designates some contamination. In another study by WHO in 1993 it
was stated that BaP concentration was 0.7 lg/L which corresponds to an excess
lifetime cancer risk of 10–5.
As a result, monitoring of these PAHs in surface water can render contributions
for potential toxic effect assessment of these pollutants as well as decision-making
for management authorities (Nikolaou et al. 2009).
PAHs Analysis
Only in the year 1990, analysis of PAHs broadened merely from BaP to a set
of 8PAHs and then 12PAHs compounds. Consequently, the analytical methods
are also advanced by employing HPLC system with UVA detector and HPLC
with florescence and GCMS detector (Pandey et al. 1999; Venkataraman et al.
1999). Method development and sample preservation for PAH analysis often
come across some limitations (Hussain 2014). In most of the investigation
of PAHs in different environmental matrices, researchers used to follow
the classical methods recommended by USEPA or methods developed by the
researchers themselves.
Ecotoxic Effects of PAHs
The toxicity of PAHs to aquatic creatures is influenced by metabolism and photo-

oxidation. Typically, in the presence of ultraviolet light, PAHs become more toxic.
Moderate to high acute toxicity of PAHs was also reported in case of aquatic life and
water birds. Apart from highly PAH-contaminated soil, terrestrial invertebrates are
not likely affected by soil PAHs. Adverse effects of PAHs to these organisms
comprise of tumors, reproduction, development, and immunity. The different routes
through which mammals can absorb PAHs include inhalation, dermal contact, and
ingestion (Dong et al. 2012; Veltman et al. 2012; Beyer et al. 2010). Moreover,
plants can also uptake PAHs from contaminated soil via roots and in turn translocate
them to other plant parts. The factors which regulate the uptake rates of PAHs by
plants include concentration, water solubility, and their physicochemical state as
well as soil type. PAH-triggered phytotoxic effects are scarce. Detailed study and
record on this are still inadequate. However, there are certain plants which contain
substances that are able to protect against PAH effects. Some plants can even
produce PAHs that function as growth hormones (Beyer et al. 2010).The levels of
PAHs found in fish and shellfish are assumed to be much higher than in the native
environment. Bioaccumulation has been also reported in terrestrial invertebrates.
Yet, metabolism of PAHs is adequate to avoid biomagnifications (Beyer et al. 2010;
Tudoran and Putz 2012).
Toxicity Analysis
In order to assess health effects of different pollutants, the toxicity equivalency factor
(TEF) methodology was put forwarded by USEPA (U.S. Environmental Protection
Agency 1993) and adapted for PAH compounds (Nisbet and LaGoy 1992). To
determine the carcinogenic potency of estimated PAHs, TEF values recommended
by Nisbet and LaGoy (Nisbet and LaGoy 1992) were used. TEFs are extensively
applied to estimate toxicities of PAH mixtures based on the toxicity of a particular
PAH compound relative to the toxicity of the reference chemical BaP. The potential
cancer risk coupled with exposure to PAH mixtures is estimated by aggregating the
concentrations of individual PAH compounds, multiplied by their TEF values. Thus,
Xn
Total BaPeq ¼ i¼1
Ci TEFi (1)
where Ci is the individual PAH concentration and TEFi is the respective toxic
equivalency factor. This method is typically employed by researchers to estimate
BaPeq toxicity of different PAHs in air, soil, and street dust. A major study from
different places in the USA revealed that the contribution of the gas-phase PAHs to the
total toxicity of the USEPA-listed 16 PAHs was larger than that of the particle-phase
PAHs (Samburova et al. 2017). The Canadian Soil Quality Guidelines (CCME 2008)
put forwarded maximum acceptable concentrations (MACs) for carcinogenic chemi-

cal compounds in soils based on an incremental risk of cancer from soil exposure
(ILCR) of 106(1 in 1 million) or 105 (1 in 100,000). This regulation was validated
for all types of land use with the recommended values of a MAC of 0.6 ng/g of BaPeq
for an ILCR of 106and a MAC of 5.3 ng/g of BaPeq for an ILCR of 105. In San
Nicolás, 41% and 60% of soil samples were observed with total BaPeq levels higher
than those established as MACs for ILCRs of 105and 106, respectively (Barran-
Berdon et al. 2012). BaPq of PAHs in industrial soil of Guwahati, India (1167 ng
BaPq/gm) (Hussain and Hoque 2015), was revealed with higher exposure risk than
traffic soil of Delhi, India(1009 ng BaPq/gm) (Agarwal 2009), soil of Shanghai, China
(892 ngBaPq/gm) (Jiang et al. 2009) [276], soil of petrochemical region of Portugal
(162.02 ng BaPq/gm) (Auqusto et al. 2012), and soil of San Nicolas, Central Mexico
(140 ng BaPq/gm) (Barran-Berdon et al. 2012). In case of street dust, rising trend of
mean BaPq level for PAHs was observed during pre-monsoon than that of monsoon
and post-monsoon season indicating high exposure risk to people from street dust of
Guwahati mainly during pre-monsoon season (Hussain et al. 2016b).
Ecosystem Risk
It is completely established that occurrence of PAHs in aquatic environment can

cause potential risk for aquatic ecosystems. In view of this, ecosystem risk assess-
ment has been employed by researchers to characterize the risk of PAHs to sur-
rounding organisms as well as the ecosystems (Wu et al. 2011). Kalf et al. (1997)
utilized risk quotient (RQ) to estimate the ecosystem risk of ten PAHs. Nevertheless,
Cao et al. (2017) advanced the method by employing the toxic equivalency factors
for the USEPA-listed 16 PAHs. This method was validated as more genuine and
logical (Cao et al. 2017). This upgraded method is often implemented by researchers
to determine ecosystem risk of PAHs in water and sediment.
Risk quotients (RQ) value designates the levels of risk posed by certain PAHs,
calculated as follows:
RQ ¼ CPAHs =CQV
Where CPAHs is the concentration of certain PAHs in the medium, CQV was the
corresponding quality values of certain PAHs in the same medium (Cao et al. 2017). In
place of quality values, the negligible concentration (NCs) and the maximum permis-
sible concentrations (MPCs) in the medium as recommended by Kalf et al. (1997) were
used by researchers (Table 4). The RQNCs and RQMPCs were represented as follows:
RQNCs ¼ CPAHs =CQVðNCsÞ
RQMPCs ¼ CPAHs =CQVðMPCsÞ

Table 4 TEF of Compounds TEF

individual PAHs
Naphthalene 0.001
Acenaphthylene 0.001
Acenaphthene 0.001
Fluorene 0.001
Phenanthrene 0.001
Anthracene 0.01
Fluoranthene 0.001
Pyrene 0.001
Benzo(a)anthracene 0.1
Chrysene 0.001
Benzo(b)fluoranthene 0.1
Benzo(k)fluoranthene 0.1
Benzo(a)pyrene 1
Dibenzo(a,h)anthracene 1
Benzo(g,h,i)perylene 0.01
Indeno(1,2,3-cd)pyrene 0.1
where CQV(NCs) was the quality values of the NCs of PAHs in the medium and
CQV(MPCs) was the quality values of the MPCs of PAHs in the same medium. The
RQPAHs, RQPAHs(NCs), and RQPAHs(MPCs) are defined as follows:
X
RQP PAHs ¼ RQi ðRQi 1Þ
X
RQP PAHsðNCsÞ ¼ RQiðNCsÞ RQiðNCsÞ 1
X
RQP PAHsðMPCsÞ ¼ RQiðMPCsÞ RQiðMPCsÞ 1
To calculate RQPAHs(NCs) and RQPAHs(MPCs) of PAHs, RQ(NCs) and

RQ(MPCs) of individual PAHs which were not less than one we only considered.
This method thus provides an approach to fully consider the ecosystem risk of
individual PAHs. Risk classifications of individual PAHs and PAHs are presented
in Tables 5 and 6 below.
The study of the water in Bharalu River, Guwahati, India, revealed RQ(MPCs) of
PAHs was >1 during both post-monsoon and pre-monsoon seasons. Value
RQ(NCs) of PAHs was also >800 during both the studied season. This signified
high ecosystem risk of Bharalu River water during both the season (Hussain 2014;
Hussain et al. 2014). Moreover investigation was also performed in Bharalu River
sediment during the same season, and it was observed that RQ(MPCs) of PAHs
was >1 during both post-monsoon and pre-monsoon season. RQ(NCs) of PAHs
during post-monsoon was >800 while during pre-monsoon was <800. This speci-
fied high ecosystem risk during post-monsoon season and moderate risk inclined
toward higher side during pre-monsoon season in Bharalu River sediment (Hussain
Table 5 Recommended RQ(NCs) and RQ(MPCs) values of PAHs(ng/gm) in water and sediment
(Cao et al. 2010)
Water Sediment
Recommended Recommended Recommended Recommended
NCs MPCs NCs MPCs
Naph 12 1200 1.4 140
Acy 0.7 70 1.2 120
Acen 0.7 70 1.2 120
Flu 0.7 70 1.2 120
Phen 3 300 5.1 510
Anth 0.7 70 1.2 120
Flan 3 300 26 2600
Pyr 0.7 70 1.2 120
BaA 0.1 10 3.6 360
Chry 3.4 340 107 10,700
BbF 0.1 10 3.6 360
BkF 0.4 40 24 2400
BaP 0.5 50 27 2700
DBA 0.5 50 27 2700
BgP 0.3 30 75 7500
IP 0.4 40 59 5900
Table 6 Risk classifications of individual PAHs and PAHs (Cao et al. 2010)
Individual PAHs RQNCs RQMPCs PAHs RQPAHs(NCs) RQPAHs(MPCs)
Risk-free 0 Risk-free =0
Low risk ≧1; <800 =0
Moderate risk ≧1 <1 Moderate risk1 ≧800 =0
Moderate risk2 <800 ≧1
High risk ≧1 High risk ≧800 ≧1
et al. 2016c). This indicates a major concern for the ecosystem of the river and
demands an urgent need for control action and remediation measures to protect the
river ecosystem.
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Water Quality Assessment of an
Unexplored Tropical Freshwater 40
System in Thiruvananthapuram,
India: A Multivariate Statistical
Approach
Anila P. Ajayan, Jan W. Rijstenbil, and K. G. Ajit Kumar
Contents
Freshwater Ecosystems: Importance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1010
Physical and Chemical Analysis in Water Quality Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1013
Statistical Methods Used in Water Quality Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1014
Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1016
Description of the Study Area and Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1016
Hydrographical Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1016
Statistical Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1018
Results and Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1018
Physical and Chemical Analysis of Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1018
Multivariate Analysis of Physical and Chemical Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1022
Cluster Analysis (CA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1023
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1027
Cross-References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1028
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1028
Abstract
Water is the life on earth. To sustain life water should be carefully managed in its
natural habitat. Several statistical methods such as multivariate analysis of data
helps within theinterpretation of complicated data matrices to understand the
water quality and ecological status of the studied systems that permits the
A. P. Ajayan (*)
Environmental Biology Division, Department of Botany, Mahatma Gandhi College, University of
Kerala, Thiruvananthapuram, Kerala, India
e-mail: anila.dehradun@gmail.com
J. W. Rijstenbil
AE3 Consultancy, Yerseke, The Netherlands
e-mail: mail@ae3.nl
K. G. Ajit Kumar
Kerala State Biodiversity Board, Thiruvananthapuram, Kerala, India

https://doi.org/10.1007/978-3-319-73645-7_30
1010 A. P. Ajayan et al.
identification of all the possible factors and sources that strongly influences the
water systems. Principal Component Analysis (PCA) and Cluster Analysis (CA)
are a reliable environmetric techniques used in water quality analysis than the
traditional comparison of physico chemical parameters. It gives better under-
standing of the water quality and ecological status of the aquatic ecosystem that is
studied. This provides the identification of all the possible factors that have an
influence on the studied aquatic body. Thus, multivariate analysis which includes
CA and PCA offers reliable tool in water resource management. The water quality
of Thiruvananthapuram Museum Lake was assessed and the results obtained
based on the PCA points out a strong influence of Nitrates, Nitrites and Phos-
phates in water quality for the study period. Based on the CA results the sampling
stations showed a clear difference in water quality. The analysis of the factor
loadings showed that Water Temperature, pH, Dissolved Oxygen, Biological
Oxygen Demand, Calcium, Total Alkalinity, Total Hardness, Magnesium, Nitrite,
Nitrate, Sodium and Potassium are the major principal components in Museum
Lake water. The present analysis of hydrographical parameters reflects the quality
of the lake water and suggests the need for proper management of the aquatic
ecosystems for conserving and preserving the quality of water and to protect that
system from allochthonous and autochthonous materials from further
deterioration.
Keywords
Museum lake · Environmetric techniques · PCA · Autochthonous · Water quality
Freshwater Ecosystems: Importance
The most common and most precious resource is indeed water on Earth. Water is the
elixir of life, all the physical events of life depend on the quality of water, and thus,
for biologists, water is the fluid of life. Our water bodies are important resources for
human civilizations since they fulfill the water demand for various uses apart from
supporting flora and fauna and improving aesthetic and landscape quality. “So much
we have, yet little is on the earth’s surface.” In the recent United Nations Sustainable
Development Goals Report (2017), globally more than two billion people are living
in countries with excess water stress. In addition to a strong water scarcity of water,
they are being polluted by various ways today. Three fourths of the Earth’s surface is
covered by water, and only less than 1% is available as freshwater for life forms. It is
a fragile resource and a seemingly inexpensive and inexhaustible one.
Freshwaters are fundamental for life on Earth, and yet freshwater biodiversity
remains poorly documented, understood, and protected. They are a major category
among the ecosystems which encompass a group of interacting organisms that
depend on one another and on the water environment for nutrients and shelter. It is
based on water, and it involves the biotic or living component (planktons, fishes,
macroinvertebrates, etc.) which in turn depends on the abiotic parameters. Freshwa-
ter ecosystems are one among them. All ecosystems that are managed or unmanaged
40 Water Quality Assessment of an Unexplored Tropical Freshwater System. . . 1011
have an important role in supporting human well-being (Millennium Ecosystem

Assessment 2005) through multiple ecosystem services including food production,
clean air and water, and cultural services, such as recreation.
Lentic ecosystems such as lakes, ponds, bogs, swamps, and pools are frequently
subject to external or internal environmental effects that bring about changes in the
biological communities as a whole. Ecologists use the term “environmental stresses”
to those effects when they impair the structure or function of food webs and other
dynamic aspects of the biological systems. Lakes are excellent habitats to study the
ecosystem dynamics: the interactions among biological, chemical, and physical
processes are frequently studied either quantitatively or qualitatively distinct from
those on land or in air (Hairston and Fussmann 2014). They interplay between
physical, biogeochemical, and organismal processes, and these studies can be put
to use in effective management. Lake ecosystems are recognized as an important
freshwater habitat that plays a significant role in maintaining freshwater biodiversity
at a landscape level. They are a unique biodiversity resource, rich in species of
plants, invertebrates, and amphibians.
The aquatic communities are not uniform in its distribution or structural and
functional characteristics as a number of environmental factors such as air tem-
perature, rainfall, or sunlight influence the individual species in that on the
temporal and spatial heterogeneity of the ecosystem. Hydrological changes as a
result of these environmental factors have an immense effect on the emergent vege-
tation, soils, and associated flora and fauna and on the robustness and the resilience of
the ecosystem, and they form an integral part in hydrography for analyzing the status
of the ecosystem considered. Hydrographic conditions determine the existence of
communities in an aquatic ecosystem, and the understanding for these parameters was
important for the dynamics of the ecosystem (Prabhakaran 2008).
The quality of living for an aquatic life depends on the water quality. Water
quality assessment generally involves analysis of physical, chemical, and biological
parameters and reflects on abiotic and biotic status of the ecosystem (IAAB 1998;
Kulshrestha and Sharma 2006; Mulani et al. 2009; Kumar et al. 2012).
Water forms the lifeblood of all the living organisms on Earth. Thus, water is a
precious renewable resource for life to exist and that must be prevented from
deterioration in quality in order to ensure a sustainable future. Water in its chemistry
is a combination of inorganic matter in ionic forms and as dissolved gases. Major
ions present in natural water include the cations Ca2+, Na+, Mg2+, and K+ and the
anions HCO3, SO42+, and Cl. The unique hydrogen bonding imparts special
properties to water that make it an essential component of life forms. Water chem-
istry is affected by climate, geology, and often autochthonous activities from the
surrounding ecosystem. The quality of water in any ecosystem provides significant
information about the available resources for supporting life in that ecosystem, and
that depends on the abiotic factors (Dhawale and Ghyare 2015). Thus, it is the urgent
need of the hour to protect the quality of water. Protecting and preserving the quality
of any water body is a significant duty of today. Even though it is inside a protected
area, the quality of the water is to be determined regularly so that measures to check
the source of pollution can be taken.
Regular water quality monitoring of water resources is necessary for sustainabil-

ity of ecosystem health and hygiene, agricultural use, and domestic and recreational
use (Pal et al. 2015). Hydrography of an aquatic body reflects the physical and
chemical properties and water quality. As physicochemical characteristics of a lake
directly have an influence on the life forms, it is important to study the hydrographical
properties. Rai (1974) has studied on the limnological properties of different rivers and
lakes in Ivory Coast. He opined that man-made lakes bring about ecological changes
which have an effect on the flora and fauna of that area and thus it is necessary to
understand the nature of that aquatic medium for efficient management.
The analysis of hydrographical parameters suggests the need for proper manage-
ment of the aquatic ecosystems for conserving and preserving the quality of water
and to protect that system from allochthonous and autochthonous materials. Loss of
aquatic habitats in their quality may lead to loss of our valuable biodiversity.
Waterbirds depend on the aquatic bodies. They are an important component of an
aquatic ecosystem.
The quantity and the quality of water determine the health of a freshwater
ecosystem sustaining numerous aquatic organisms in addition to the requirements
in various industrial, domestic, and agricultural sectors. For healthy ecosystem, an
effective management of both quantity and quality of water resources is required.
These natural resources are increasingly under threat as they face the brunt of
impacts of human activities, autochthonous organic matter, and activities by urban-
ization. In order to function properly and to keep our freshwater resources healthy, an
effective management through quality assessment of water resources is needed.
Globally, India covers about 4% of the freshwater resources in the world. Inland
water bodies and their hydrology have attracted the attention of various researchers
from 1949. The hydrobiology of Adyar River was studied by Chacko and Ganapati
(1949). Rao and Govind (1964) made a study on the hydrology of Tungabhadra
reservoir. Hydrological studies of various water bodies have been carried out by
many workers like Munawar (1970), Ajmal et al. (1985), Azis and Synudeen (1989),
Kumary and Azis (1992), Jeyasingh (1997), Menon et al. (2000), Mini et al.
(2003), Ida (2004), Rajakumar et al. (2006), Jacob et al. (2008), Raj and Azeez
(2009), Joseph et al. (2010), Sheela et al. (2011), Dhinamala et al. (2015), and Reddy
and Parameshwar (2016). Hydrological studies reflect the water quality of that
aquatic body, and it is important because it maintains the ecological processes that
support biodiversity. However, decline in the water quality that poses environmental
changes is a major threat to the stability of the biota. Although considerable works
have been carried out on the hydrology of different water bodies in India, there are
still numerous inland water bodies that remain scientifically unexplored. Monitoring
physical and chemical parameters for water quality has attained greater importance
and is important in ecosystem assessment of aquatic bodies.
Increased pollution level in the water contributes to health hazards and leads to
deterioration of the ecosystem (Joseph et al. 2010), and it is the urgent need of the
hour to protect the quality of water. On the other hand, in case of pristine aquatic
systems, such studies shall contribute toward the protection and preservation of its
good water quality (Muniyan and Ambedkar 2011). Protecting and preserving the
quality of any water body is a significant duty of today. Even if it is inside a protected
area, the quality of the water is to be determined regularly so that measures to check
the source of pollution can be taken.
Physical and Chemical Analysis in Water Quality Study
The environmental factors considered in water quality study are temperature (atmo-
spheric and surface water), pH, total dissolved solids (TDS), electrical conductivity,
dissolved oxygen (DO), biological oxygen demand (BOD), chemical oxygen demand
(COD), total alkalinity, total hardness, and nutrients such as phosphate, nitrite-nitrogen
(NO2-N), and nitrate-nitrogen (NO3-N) and main ionic components of water like
sodium (Na+), potassium (K+), calcium (Ca2+), magnesium (Mg2+), and silicate
(SiO2-Si). Each parameter has its own importance in influencing the quality of water.
Water temperature is an important physical parameter that influences the aquatic
biota in their behavior and metabolism, whereas pH of water is influenced by a
number of factors such as precipitation, photosynthesis, and respiration by aquatic
flora and fauna, weathering of mineral rocks, etc. This determines the solubility
(amount that can be dissolved in the water) and biological availability (amount that
can be utilized by aquatic life) of chemical constituents such as nutrients (phosphorus,
nitrogen, and carbon) (Prabhakaran 2008).
Combined total of inorganic salts such as calcium, magnesium, potassium,
sodium, bicarbonates, chlorides, and sulfates and some small amounts of organic
matter that are dissolved in water determines the total dissolved solids (TDS) in
water. Their presence originates from natural sources, sewage, urban runoff, indus-
trial wastewater, or chemicals used in the water treatment processes. An elevated
TDS concentration is not a health hazard as it is only a secondary drinking water
standard. At the same time, it must be regulated because it is more of an aesthetic
rather than a health hazard as TDS above 300 mg/l in freshwater may become
“brackish” and some species with a low salinity tolerance will be outcompeted by
salt-tolerant species.
Dissolved oxygen is indicative of the health of an aquatic system. It is the vital
metabolism of aerobic organisms. Low DO values are bad for aquatic animals,
whereas too high DO inhibits photosynthesis too. Respiration depends purely on
the amount of oxygen dissolved in the water produced by the metabolic activity of
heterotrophic microbes and fauna as well as the algae and submersed plants.
Optimum concentration of dissolved oxygen is essential for maintaining aesthetic
qualities of water as well as for supporting life. Rajani et al. (2016) found that
organic matter exhibited an inverse relation with dissolved oxygen, and this trend
has been confirmed in their physicochemical and phytoplankton study of Fox Sagar
Lake in Hyderabad as dissolved oxygen is used in decomposition of organic matter
which was accelerated at high temperatures.
Biological oxygen demand (BOD520) is used as the index of organic pollution of
wastewater that can be decomposed by bacteria under anaerobic conditions (Sladeck
et al. 1982). It is a measure of degradable organic matter in water. BOD within the
range 1–5 mg/l demonstrates moderate water quality. BOD indicates the presence of
microbial activities on the dead organic matter present in aquatic body. During
monsoon, surface runoff carries waste and sewage from the surrounding areas into
the low-lying beds of the lake thereby increasing the respiratory activity of the
heterotrophic organisms which confirms the reason for low DO and high BOD
during monsoon.
Chemical oxygen demand (COD) is the measure of oxygen in water that is
consumed by the microbes during the oxidation of organic matter by a strong
oxidizing agent. High COD indicates the presence of all forms of organic matter,
both biodegradable and non-biodegradable, and hence the degree of pollution in
waters (Krishnan 2008). This includes both biologically inert organic matters.
Therefore, COD values are usually higher than the BOD values. A higher value of
COD in water indicates the presence of chemically degradable organic pollutants.
Most open Indian ponds have higher chemical oxygen demand with maximum
values in summer season (Kaushik et al. 1991). The higher values of COD are due
to the decreased water temperature, low water volume, and increased evaporation
rate (Koshy and Nayar 1999; Yadav and Srivastava 2011). The presence of chem-
ically oxidizable organic matters like nitrates, nitrites, and sulfates also enhances the
concentration of COD in water.
Total alkalinity in the water samples is primarily a function of carbonate, bicar-
bonate, and hydroxide content. It is the measure of buffering capacity of water. It is
important to assess the alkalinity of water bodies to determine the ability of neutral-
izing the acidic pollution of water from rainfall of wastewater. To be precise,
alkalinity does not refer to pH but the ability of water to resist change in pH. As
far as an aquatic ecosystem is considered, changes in alkalinity directly affect the
living organisms there. Alkalinity has indirect effects on primary productivity or
phytoplankton growth. In low-alkalinity aquatic environments, certain nutrients are
unavailable to aquatic plant life (Wurts 2002). Harney et al. (2013) analyzed the
seasonal variations of hydrographical parameters of Pindavani pond of Central India.
In their study, the total alkalinity was minimum in summer and maximum in
monsoon. They concluded that minimum values of total alkalinity during winter
and summer are due to assimilation of bicarbonates by the pond biota directly for
their load which leads to the depletion of bicarbonates in water which results in low
values of total alkalinity.
Total hardness is used to describe the effect of dissolved minerals especially Ca
and Mg, confirming the suitability of water for domestic, industrial, and drinking
purposes, which is attributed to the presence of calcium and magnesium as bicar-
bonates, sulfates, chloride, or nitrates.
Statistical Methods Used in Water Quality Assessment
Several statistical methods like multivariate analysis of data help in the interpretation
of complex data matrices to better understand the water quality and ecological status
of the aquatic systems. It allows the identification of possible factors and sources that
influence water systems (Kane and Lazo 2015). Principal component analysis (PCA)
and cluster analysis (CA) are reliable environmetric techniques used in water quality
analysis than the traditional comparison of physicochemical parameters. This pro-
vides the identification of all the possible factors that have an influence on the
studied aquatic body. Thus, multivariate analysis which includes CA and PCA offers
a reliable tool in water resource management (Vega et al. 1998; Alberto et al. 2001;
Wunderlin et al. 2001; Reghunath et al. 2002; Simeonova et al. 2003; Tariq et al.
2005; Lee et al. 2006; Shrestha and Kazama 2007 Bhuiyan et al. 2011; Pearce et al.
2013; Machado et al. 2014; Wang et al. 2014; Zeng and Arnold 2014; Ndungu et al.
2014, Muangthong and Shrestha, 2015; Rana and Gupta 2016; Ling et al. 2017;
Singh and Manaan 2017).
PCA was carried out to extract the major factors in the physical and chemical
parameters that influence the water chemistry. This analysis reduces the original
variables to a lower number of linear combinations, identifying the components that
have greater impacts on the data variability (de la Lanza-Espino et al. 1998). Along
with the extraction of data information to some extent and the temporal clustering of
samples, PCA could also explain the different characteristics and their relationship
between different variables by the variable lines. PAST v. 3.10 was used to carry out
the PCA to determine the main principal components from the original variables.
The eigenvalues in PCA denotes the significance of the components. Any factor with
an eigenvalue greater than 1 is considered significant (Bhat et al. 2014). The first PC
represents largest variability in the original dataset (Zare Gariji et al. 2011). The
higher the loading of a variable, the more that variable contributes to the variation
accounted for by the particular principal component (Abdul-Wahab et al. 2005). In
practice only loadings with absolute values greater than 50% are selected for the
principal component interpretation (Jollife 1986). Based on their absolute magni-
tude, component loading values greater than 0.75, between 0.75 and 0.5, and
between 0.5 and 0.3 are classified as strong, moderate, and weak, respectively
(Nair et al. 2010; Manoj et al. 2013).
Cluster analysis (CA) is a classification technique which can be used to determine
the existence of natural subgroups or classes of individuals, and they are grouped
based on their similarities or dissimilarities (Kumar and Padhy 2014). Cluster
analysis uncovers intrinsic structure or underlying behavior of a dataset without
making a priori assumptions about the data (Ndungu et al. 2014). It also provides a
visual summary of intra-relationship among the water quality parameters and assists
in better understanding of controlling factors (Pejman et al. 2009). Brogueira and
Cabecadas (2006) analyzed the environmental status of Tagus estuary using multi-
variate analysis. They concluded that the cluster analysis is useful in solving
classification problems, whose objective is to place factors or variables into groups
such that the degree of association is strong between members of the same cluster
and weak between members of different clusters.
In this chapter, the temporal variations and interactions of hydrographical param-
eters of Museum Lake are discussed. Multivariate statistical analyses of the param-
eters are used to determine the interrelationship between various water quality
parameters of the aquatic body. Despite Museum Lake being under the management
of the Department of Museums and Zoo in Kerala, no serious studies are taken on the
ecosystem assessment of this water body leading to its further protection. So with the
multivariate statistical analysis on the water quality of this lake, we aim to provide
baseline information about the major causes of pollution.
Methods
Description of the Study Area and Sampling
The description of Museum Lake has been provided in various publications (Ajayan
et al. 2015; Ajayan and Kumar 2016; Ajayan et al. 2016). Therefore only a brief
description is given here. Museum Lake, a shallow lake, is generally deep with the
marginal slope ranging from 3 to 6 m. It is a perennial water body yet an artificial
one, and for 157 years since its construction in 1859, it has never lost its water level
even in the scorching summers. The expansive lake inside the Thiruvananthapuram
Zoological Garden – complete with an island, lush vegetation with huge population
of bats, and the consequent abundance of winged visitors – has never failed to arrest
the attention of the zoo tourists. This is a source of water for the zoo animals. Even
though the zoo has a general policy that bans plastics inside, careless throwing of
plastic bottles and carry bags is often a threat to this aquatic ecosystem. The location
map showing the study area is given in Fig. 1.
Monitoring the lake water quality helps to reduce further degradation and imple-
ment measures to check degradation. In this perspective, the present study provides a
baseline diagnosis of the water quality of the Museum Lake with multivariate
analysis.
In order to study the seasonal variations in the environmental parameters, water
samples were collected monthly for two consecutive years, and the monthly data
were divided into three seasons as:
Year 2013 2014

Pre-monsoon (February–May) PreM1 PreM2
Monsoon (June–September) Mon1 Mon2
Post-monsoon (October–January) PoM1 PoM2
Hydrographical Parameters
Water samples were collected from the Museum Lake for a period from February
2013 to January 2015. For the collection and preservation of water samples for
different laboratory analyses such as Total Dissolved Solids (TDS), Electrical
Conductivity (EC)-(Conductivity meter MK 509 calibrated with 0.01M KCl.),
Chemical Oxygen Demand (COD)-(Open Reflex Method), Total Alkalinity (TA)-
(Sulphuric acid Titrimetric method), Total Hardness (TH)-(EDTA Titrimetric
Fig. 1 Location map of Museum Lake, Thiruvananthapuram
Method) and nutrients such as Phosphate (PO43)-(Ascorbic acid Spectrophoto-

metric method), Nitrite (NO2)-(Sulphanilamide Spectrophotometric method)
and Nitrate (NO3)-(Cadmium reduction column method) and main ionic com-
ponents of water like Silicate-(Ammonium molybdate Spectrophotometric
method), Sodium, Potassium-(digital Flame photometer Type 130), Calcium
(Ca2+) and Magnesium (Mg2+)-(EDTA Titrimetric method) in separate 1 l acid
cleaned and pre-labeled polythene bottles following the standard methodology
prescribed by APHA (2005) and Trivedi and Goel (1986). pH and temperature of
the water were measured at the site itself using a portable pH meter and a
thermometer of the range 0–50 C and 0.1 C accuracy. For the measurement of
dissolved oxygen (DO) and biological oxygen demand (BOD), separate 300 ml
clean glass stoppered BOD bottles were used for sample collection (standard
volumetric Winkler’s method).
Meteorological data such as rainfall data were collected from the India Meteoro-
logical Department, Thiruvananthapuram.
Statistical Analysis
Statistical programs like PRIMER (Plymouth Routines in Multivariate Ecological

Research, version 6.1.9) and PAST (PAleontological STatistics version 3.10) were
used formultivariate analysis of data.
Results and Discussions
Physical and Chemical Analysis of Water
The meteorological parameter considered was rainfall. The southwest (Mon1 and
Mon2) and the northeast monsoons (PoM1 and PoM2) play a major role in the
climate and on the water level of the Museum Lake. The range of rainfall was
30.5–499.0 mm during 2013–2014 study periods, and the average rainfall was
158.0 mm. For the study period 2014–2015, the range of rainfall was between 3.5
and 526.4 mm, and the average rainfall was 161.3 mm. Seasonal variations of
rainfall for the study period are shown in Fig. 2.
The mean variations (MeanSD) of the hydrographic parameters for the 2-year
study periods are given in the Tables 1 and 2, respectively.
During the entire study period, the range of temperature was 22–25 C
(Av. = 23 C). A low fluctuation of water temperature is due to the shade provided
by the riparian trees which prevents the sun’s rays to hit the surface water and thus
reduces the water temperature. Rai (1974) was of the opinion that there will be little
variation in temperature of the man-made lakes with a small difference in temper-
ature between the surface and the bottom.
Year 1
300
Year 2
250
200
150
100
50
0
PreM Mon PoM
Fig. 2 Seasonal variations in total rainfall (in mm) for Thiruvananthapuram City (Zoo) during the
2-year study period (Courtesy: Indian Meteorological Department, Thiruvananthapuram)
Table 1 Means and variations (MeanSD) of the hydrological parameters in the Museum Lake
for year 1 (2013–2014)
Parameters Pre-monsoon (PreM1) Monsoon (Mon1) Post-monsoon (PoM1)
Water temperature 23.7 1.5 23.25 0.5 23 0.82
pH 6.9 0.42 6.8 0.34 6.9 0.52
DO 11.29 10.98 8.28 4.02 8.08 5.11
BOD 10.07 10.11 8.29 4.29 6.00 5.45
COD 43.60 16.30 30.08 9.67 43.35 10.35
Total alkalinity 21.56 2.99 16.63 3.38 17.35 1.27
Nitrate-nitrogen 1.73 1.55 3.99 1.54 2.60 0.07
Nitrite-nitrogen 0.39 0.30 0.90 0.21 0.22 0.18
Calcium 13.4 5.95 18.65 3.59 17.23 3.05
Total hardness 69.44 26.76 62.59 8.22 63.25 30.54
Magnesium 13.30 5.30 14.11 5.88 11.03 6.77
Phosphate 6.87 3.22 3.46 2.12 1.43 0.91
Silicate 5.35 5.19 8.06 3.35 9.72 3.00
Sodium 4.88 2.17 4.94 1.22 5.13 1.05
Potassium 6.16 4.48 12.24 10.81 11.68 11.48
TDS 76.30 7.35 77.72 3.47 76.41 10.46
Conductivity 156.20 6.28 147.10 8.16 153.88 6.05

(WT, C; DO, BOD, COD, TA, NO3N, NO2N, Ca, Mg, TH, Phos, Na, Sili, and K, mg/l; TDS and
conductivity, m mho)
Table 2 Means and variations (MeanSD) of the hydrological parameters in the Museum Lake
for year 2 (2014–2015)
Parameters Pre-monsoon (PreM2) Monsoon (Mon2) Post-monsoon (PoM2)
Water temperature 24 0.96 23 0.82 23 0.82
pH 7.05 0.58 6.8 0.32 6.6 0.2
DO 6.10 3.33 7.2 3.71 4.88 2.06
BOD 5.31 3.50 6.79 5.1 3.48 0.66
COD 38.47 15.32 36.09 10.44 45.87 6.20
Total alkalinity 15.18 7.65 17.19 2.67 16.69 0.90
Nitrate-nitrogen 4.10 4.70 3.03 0.77 2.88 2.37
Nitrite-nitrogen 0.38 0.36 0.58 0.24 0.14 0.02
Calcium 13.38 4.61 19.54 5.78 13.79 1.91
Total hardness 30.48 12.59 62.41 12.69 61.23 0.54
Magnesium 4.52 3.62 10.45 4.45 11.32 3.59
Phosphate 2.79 1.13 3.67 1.91 1.66 0.53
Silicate 8.31 5.43 6.5 2.55 6.27 2.75
Sodium 4.17 1.68 8.3 2.56 6.31 0.54
Potassium 4.82 5.43 3.56 0.85 13.32 9.60
TDS 75.73 7.03 72.01 6.65 71.55 3.56
Conductivity 160.68 13.12 137.67 8.35 144.79 16.43

(WT, C; DO, BOD, COD, TA, NO3N, NO2N, Ca, Mg, TH, Phos, Na, Sili, and K, mg/l; TDS and
conductivity, m mho)
The pH is an important parameter in water which influences aquatic production.

In the present study, it was between ranges of 6.5 and 7.6. A slight acidic pH was
recorded during the rainy months. The slight acidic pH of water during the rainy
months is due to the seepage of rainwater and resultant dilution of the lake water.
This result is in agreement with the results of Radhika et al. (2004). A pH range of
6.5–8.5 is suitable for aquatic life and the best for water in quality for different
purposes. The standard concentration of DO for aquatic organisms to survive is
>5 mg/l (Boyd 1998). In the present study, the DO was within this standard
concentration with average DO values for the 2-year study period being 9.2 and
6.05 mg/l, respectively.
During the present study, the average values for BOD for the 2-year study period
were 8.12 and 5.19 mg/l. BOD is the amount of oxygen required for the microorgan-
isms to decompose organic materials present in water. A higher BOD level represents
degradation of the water quality that reduces the dissolved oxygen concentration
thereby making unsuitable for the aquatic lives to survive. In the present study, highest
BOD level was recorded during the Mon1. Museum Lake is surrounded by lush
vegetation, and the water body is covered with uprooted bamboo trees and leaf litter
from them. A higher BOD may be due to the degrading activity of microorganisms
there. The similar observation was made by Jacob et al. (2008) in Veli Lake.
COD values are indicative of the presence of chemically oxidizable carbonaceous
matter like nitrates, nitrites, and sulfates (Chandra et al. 2010). The average value of
COD for the entire study period was 6.75–73.25 mg/l which may be due to the input
of chemically oxidizable nitrates in the form of organic wastes from the bat feces. A
similar result was also recorded by Singh et al. (2016) from river Narmada.
In natural water, alkalinity is due to the salts of carbonates, bicarbonates, borates,
silicates, and phosphates along with the hydroxide ions in free state (Ramachandra
and Solanki 2007). An alkalinity value above 100 mg/l for an aquatic body is
indicative of highly productive ecosystem. It is also useful in determining the
water quality in pollution perspective. During the present study, the average value
for alkalinity was in the range of 9.5–27 mg/l.
During year 1, the MeanSD for nitrate-nitrogen was 1.73 1.55 for
pre-monsoon, 3.99 1.54 for monsoon, and 2.60 0.07 for post-monsoon. The
MeanSD for year 2 are 4.10 4.70, 3.03 0.77, and 2.88 2.37 for the three
study seasons. A higher concentration of nitrate during the monsoon season resulted
from the cumulative effect of rainfall and subsequent land draining. Similar results
were recorded from the studies by Kumar (1998) and Singh et al. (2016). The mean
average nitrite-nitrogen recorded for the study period was 0.43 mg/l. The presence of
nitrite indicates fresh input of organic load into the water system. It is the partially
reduced form of nitrogen and is found in small quantities.
The average value of total hardness for the study period was 58.29 mg/l. The
MeanSD obtained was 69.44 26.76 for PreM1, 62.59 8.22 for Mon1, and
63.25 30.54 for PoM1. For PreM2 the Mean SD was 30.48 12.59, while for
Mon2 and PoM2, it was 62.41 12.69 and 61.23 0.54, respectively.
The hardness of water is imparted by the ions of calcium and magnesium in
combination with its carbonates and bicarbonates. Based on the amount of hardness,
water can be classified as soft if 0–60 mg/l , moderately hard if 61–120 mg/l, hard if
102–160 mg/l, and very hard if greater than 180 mg/l. In the present study, total
hardness values ranged from 20.5 to 93 mg/l which denotes that Museum Lake has
moderately hard water.
As the content of Ca and Mg in water increases, the content of hardness also
shoots up (Skipton and Dvorak 2009). The average value of calcium hardness for the
study period was 15.98 mg/l, whereas the average value for Mg2+ recorded was
10.79 mg/l for the study period. Calcium and magnesium are the dominant cations in
an aquatic body. The concentrations of calcium and magnesium were found high
during monsoon and low during pre-monsoon period. Higher concentration of
calcium and magnesium is due to the dissolution of carbonate minerals in water
through rainwater mixing, while a lower concentration is due to increased photo-
synthetic activity of aquatic organisms (Divya 2013).
The average phosphate concentration recorded during the study period was
3.3 mg/l. Since it binds with soil, organic matter, and sediment particles, it is
rarely found in high concentrations in freshwaters. Decomposition of dead
plants and animals adds organic phosphorus in water (Singh et al. 2013).
During the study period, the phosphate concentration ranged from 0.78 to
14.68 mg/l.
Silicates are an important nutrient for an aquatic ecosystem as they significantly
influence phytoplankton growth especially the diatoms. A higher concentration of
silicates has been recorded from Museum Lake during the present study. The
degradation of plant tissue is a major source of dissolved silica in water (Harriss
1967). The silicate concentration recorded for the entire study period showed an
average value of 7.37 mg/l. Moreover, the uprooted plant debris and dead macro-
phytes are also a source of dissolved silica in Museum Lake for its higher
concentration.
The sodium concentration ranged between 3.25 and 9.25 mg/l, whereas the
average value for potassium recorded was 8.63 mg/l during the study period.
Mon2 marked higher concentration of potassium, and PreM2 recorded lower potas-
sium content. Similar results were obtained by Kamble et al. (2008). A peak increase
of potassium was noticed during the rainy monsoon and post-monsoon period. This
may be due to rain runoff of decomposed plant materials from surrounding vegeta-
tion and organic wastes from the bat population which help in increasing the
concentration of potassium in the water. Our results are in agreement with Singh
et al. (2013).
The average concentration of TDS for the study period was 74.95 m mho. It is
consisted of inorganic salts, small amounts of organic matter, and dissolved mate-
rials. The average value for conductivity recorded was 150.05 m mho. Conductivity
is a measure of capacity of water to conduct electric current. Electrical conductivity
increases with the increase in ion content in water, and thus changes in ionic
concentrations are reflected in water. Here also there was a fluctuation in conduc-
tivity during monsoon with lower value and a higher concentration during post-
monsoon. The lower concentration can be attributed to the heavy water influx due to
rainfall and resultant dilution of the salts in water.
Multivariate Analysis of Physical and Chemical Parameters
Principal Component Analysis (PCA)

PCA is a powerful pattern recognition technique that aims to reduce multi-
dimensionality of datasets (Kumar and Padhy 2014). The eigenvalues of the princi-
pal components are a measure of their associated variances (Meglen 1992; Wenning
and Erickson 1994; Ndungu et al. 2014). The newly obtained results in lower
dimensions (principal components, PCs) simplify data interpretation (Singh et al.
2004; West 2009).
In the present study, PCA was conducted for two separate years (year 1 and year 2).
PCA for Year 1

Based on the eigenvalues scree plot, the 18 physicochemical parameters were
reduced to two main principal component factors (PC 1 and PC 2) from the
leveling-off points in the scree plot. The largest eigenvalue corresponds to 12.05
which accounts for 68.86% of the total variance. It comprised of the parameters
water temperature, pH, DO, BOD, COD, total alkalinity, total hardness, magnesium
hardness, phosphate, and conductivity. The second factor corresponding to the
second eigenvalue 5.96 accounts for approximately 33.13% of the total variance
with water temperature, DO, BOD, total alkalinity, nitrate, nitrite, calcium hardness,
total hardness, magnesium hardness, phosphate, TDS, and rainfall. The remaining
factors have eigenvalues of less than unity. The correlation matrix of the variables
and the factor loadings represent the nature of variations and the influential patterns.
The actual eigenvalue and the percentage of cumulative variance are shown in
Fig. 3, and Table 3 summarizes the corresponding eigenvectors.
The bi-plot of the first and second PCs (Fig. 4) showed that water temperature,
DO, BOD, phosphate, total hardness, and total alkalinity had a strong influence
on the water quality during PreM1. This confirms the degrading activity of
67.5 Eigenvalue
60.0
% Variance
52.5
45.0
37.5
30.0
22.5
15.0
7.5
0.0
PC 1 PC 2
Fig. 3 The actual eigenvalue and the percentage of cumulative variance of PCA year 1
Table 3 Eigenvectors of principal components for PCA year 1

PC 1 PC 2 PC 1 PC 2
WT 0.82092 0.57104 TH 0.98265 0.18548
pH 0.91158 0.41112 MgH 0.03961 0.99922
DO 0.96013 0.27956 Phos 0.82211 0.56933
BOD 0.68119 0.73211 Sili 0.81777 0.57555
COD 0.69185 0.72205 Na 0.50382 0.86381
TA 0.99696 0.077949 K 0.98964 0.1436
NO3 0.90974 0.41519 TDS 0.73169 0.68164
NO2 0.48691 0.87345 Cond 0.84091 0.54118
CaH 0.99932 0.036998 Rainfall 0.90609 0.42309
microorganisms on the uprooted bamboo trees and leaf litter from the surrounding
vegetation in Museum Lake. During Mon1, the parameters that influenced the
water chemistry were nitrates, nitrites, and TDS along with rainfall which confirms
the rainwater mixing of organic wastes and subsequent land draining. For
PoM1, sodium, potassium, and silicates showed a considerable influence on the
water quality.
PCA for Year 2

The PCA for Year 2 showed a slight variation in water chemistry for the water body.
Like year 1, two main principal component factors (PC 1 and PC 2) were derived. PC
1 corresponded for highest eigenvalue of 10.45 with a percentage of variance 58.06%.
DO, BOD, COD, total alkalinity, nitrite, calcium hardness, total hardness, magnesium
hardness, phosphate, sodium, potassium, and rainfall were the parameters for PC
1. The lowest eigenvalue corresponded was 7.54, and the cumulative variance was
41.94%. It comprised of water temperature, pH, DO, BOD, total alkalinity, nitrate,
nitrite, calcium hardness, phosphate, silicate, sodium, TDS, and rainfall.
The actual eigenvalue and the percentage of cumulative variance are shown in
Fig. 5, and Table 4 summarizes the corresponding eigenvectors.
During the year 2, TDS, silicate, nitrate, and water temperature showed a strong
influence over water chemistry for PreM2. During Mon2 there was a strong corre-
lation between DO, BOD, phosphate, and nitrite which is very clearly shown in the
bi-plot (Fig. 6). Calcium hardness, rainfall, sodium, and total alkalinity also had an
influence over the water chemistry during Mon2. PoM2 was slightly influenced by
total hardness, magnesium hardness, potassium, and COD.
Cluster Analysis (CA)
The multivariate statistical measure cluster analysis of the present study on the water
chemistry resulted in temporal variations. CA was used to find out the similarity in
1024
Fig. 4 Bi-plot of the principal components showing correlation PCA year 1

A. P. Ajayan et al.
60.0
Eigenvalue
52.5
% Variance
45.0
37.5
30.0
22.5
15.0
7.5
0.0
PC 1 PC 2
Fig. 5 The actual eigenvalue and the percentage of cumulative variance of PCA year 2
Table 4 Eigenvectors of principal components for PCA year 2

PC 1 PC 2 PC 1 PC 2
WT 0.99573 0.092313 TH 0.99823 0.05953
pH 0.83779 0.54599 MgH 0.97797 0.20872
DO 0.067297 0.99773 Phos 0.020756 0.99978
BOD 0.039996 0.9992 Sili 0.98175 0.19019
COD 0.1928 0.98124 Na 0.9182 0.39611
TA 0.98875 0.14956 K 0.3062 0.95197
NO3 0.97898 0.20397 TDS 0.98144 0.19176
NO2 0.039996 0.9992 Cond 0.97707 0.21291
CaH 0.63612 0.77159 Rainfall 0.77452 0.63254
water chemistry between the three seasons for the study period. The dendrogram was
generated by grouping the months on the basis of percentage of similarity and
dissimilarity of the physical and chemical parameters which is presented in Fig. 7.
Seasonally the cluster analysis resulted in three distinct clusters – Cluster I (PoM1
and PoM2), Cluster II (PreM1 and PreM2), and Cluster III (PoM1and PoM2). The
analysis of the similarity of study seasons is carried out to indicate relationship
intensity between seasons as cluster. The Bray-Curtis similarity analysis results show
that there is 97% similarity between the two post-monsoon periods, whereas there is
95% similarity between Mon1 and Mon2. Between monsoon and post-monsoon
seasons, there was a 94% similarity. There was 92% dissimilarity between
pre-monsoon and both the rainy seasons. The results of cluster analysis revealed
that both the rainy seasons had similar organic nutrient load, whereas pre-monsoon
period showed less, and it is clearly shown in Fig. 7.
1026
Fig. 6 Bi-plot of the principal components showing correlation PCA year 2

A. P. Ajayan et al.
Group average
90 Transform: Square root

Resemblance: S17 Bray Curtis similarity
92
Similarity
94
96
98
100
PoM1
PoM2
Mon1
Mon2
PreM1
PreM2
Samples
Fig. 7 Dendrogram of the cluster analysis showing seasonal variations in water quality
Conclusion
Hydrographical data can be used to determine the ecosystem dynamics and the
existence of communities associated with that ecosystem. Museum Lake enjoys a
tropical and moderate climate that determines the hydrographic properties and
abundance and distribution of various organisms in and around it. A low fluctuation
of water temperature recorded is due to the shades of riparian trees along the lake. A
slight acidic pH of water recorded during the rainy months is due to the seepage of
rainwater and resultant dilution of the lake water.
The pH range was well within the limits for aquatic organisms to survive. In the
present study, the dissolved oxygen was within this standard concentration pre-
scribed for the aquatic organisms to survive. A higher BOD level recorded was
due to the degradation of uprooted bamboo trees and the leaf litter from the adjacent
riparian vegetation by the degrading activity of the microorganisms there. Highest
BOD noticed during the rainy seasons confirms the rainwater seepage into the lake
and mixing of organic wastes through this. Higher concentration of COD was
noticed which is indicative of the presence of chemically oxidizable carbonaceous
matter like nitrates and nitrites, and in Museum Lake, it is due to the input of
chemically oxidizable nitrates in the form of organic nitrites from bat feces. A
slightly higher concentration of nitrate was recorded during the study period which
resulted from the cumulative effect of rainfall and subsequent land draining. The
presence of nitrite indicates fresh input of organic load into the water system.
The result of total hardness of water denotes that Museum Lake has moderately
hard water. Higher calcium and magnesium concentration which was recorded
during monsoon period was due to the dissolution of carbonate minerals in water
through rainwater mixing, while a lower concentration which was recorded during
pre-monsoon period may be due to increased photosynthetic activity of aquatic

organisms. Comparatively high concentrations of phosphate, sodium, and potassium
were recorded from Museum Lake. The main sources of sodium and potassium are
from dead plants and animal materials and are bound in clay, and the decomposition
of dead plants and animals adds organic phosphorus in water.
The PCA results for year 1 revealed that water temperature, DO, BOD, total
alkalinity, nitrate, nitrite, total hardness, sodium, potassium, phosphate, TDS, sili-
cate, and rainfall are the influential factors for water chemistry of Museum Lake. The
strong correlation noticed between nitrate and rainfall confirms the rainwater mixing
of organic wastes into the lake water. For year 2, the most influencing parameters
were identified as nitrate, nitrite, rainfall, calcium hardness, sodium, potassium,
silicate, phosphate, total alkalinity, total hardness, magnesium hardness, COD,
DO, BOD, and water temperature. From the analysis of hydrographical parameters,
it is confirmed that phosphates, nitrates, water temperature, and rainfall are influenc-
ing the lake water chemistry. The allochthonous sources of pollution identified are
bat feces and degrading leaf litter fallen from the riparian vegetation.
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Nanomembranes for Environment
41
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1035
Vision, Mission, and Aim of the Present Treatise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1035
Scope of the Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1036
Introduction to the Application Area of Nanomembranes in
Environmental Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1036
Wide World of Application of Nanomembranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1037
Wastewater Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1038
Chemical Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1039
Food Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1039
Biotechnology and Medical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1039
Fabrication and Mechanism of Separation in Nanomembranes . . . . . . . . . . . . . . . . . . . . . . . . . . . 1040
Science, Human Mankind, and the World of Environmental Sustainability . . . . . . . . . . . . . . . . . . 1040
Nanotechnology, Sustainability, and the Vision for the Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1041
Scientific Research Pursuit in the Field of Nanomembranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1042
Carbon Nanotube-Based Membranes for Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1044
Nano-biomembranes and Environmental Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1044
Nanocomposite Membranes for Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1045
Polymer Nanomembranes for Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1045
The Future of Nanomembranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1045
Vision of Nanotechnology in the Treatment of Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1046
Water Pollution and Nanofiltration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1046
Desalination, Future of Water Science, and the Wide Progress of Nanomembranes . . . . . 1047
Suitability of the Nanomembrane Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1048
S. Palit (*)
Department of Chemical Engineering, University of Petroleum and Energy Studies, Energy Acres,
Dehradun, Uttarakhand, India
e-mail: sukanchan68@gmail.com; sukanchan92@gmail.com
C. M. Hussain
Department of Chemistry and Environmental Sciences, New Jersey Institute of Technology,
Newark, NJ, USA

https://doi.org/10.1007/978-3-319-73645-7_31
Nanofiltration Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1049

Nanocatalysts and Magnetic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1049
Vision Behind Sensing and Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1050
Increasing Potable Water Supplies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1050
Desalination of Seawater and the Vast Future of Science . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1050
Safety of Industrial Effluent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1050
Benefits of Nanotechnology and the Scientific Vision and Scientific Comprehension . . . . . . . 1051
Regulation of Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1051
Scientific Validation and Technology Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1051
Nanotechnology Risk Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1052
Technology Validation, Scientific Introspection, and Vision for the Future
in Nanomembranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1052
Environmental Sustainability, Application of Membrane Science, and the Wide World
of Nanomembranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1053
The Challenge and True Vision of Environmental Engineering Separation Processes . . . . . . . 1053
Nontraditional Environmental Engineering Techniques and Membrane Science . . . . . . . . . 1054
The Challenge and Vision of Scientific Validation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1054
Future Environmental Perspectives and Vision of Application of Nanomembranes . . . . . . . . . 1055
Future Dimensions and Future Trends in the Application of Nanomembranes . . . . . . . . . . . . . . . 1055
Summary and Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1055
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1056
Abstract
The world of environmental engineering science in today’s world is undergoing
drastic and visionary challenges. Vision of science, progress of human civiliza-
tion, and the fruits of technology are the torchbearers of greater emancipation and
true realization of environmental engineering science. Membrane separation
processes and novel separation science are not immature yet visionary avenues
of science. Scientific endeavor in nanofiltration and nanomembranes needs to be
readdressed and reenvisioned at each step of human research pursuit. Application
of nanomembranes in environmental engineering is a vibrant and visionary area
of science. Industrial wastewater treatment and drinking water treatment are the
application areas of nanomembranes. The question of environmental sustainabil-
ity and the application of membrane science in environmental engineering sci-
ence are of immense relevance to the progress of human civilization and the
greater emancipation of science. Science and engineering are a colossus without a
will of its own in today’s human civilization. True emancipation of environmental
engineering science and realization of environmental sustainability are the urgent
need of the hour. Human scientific research pursuit today stands in the midst of
scientific revelation and true greatness. The authors pinpoint the immense poten-
tial of nanomembranes in environmental application with a keen eye toward
attainment of environmental sustainability. The tryst with scientific destiny is
widely observed at each step of this scientific research pursuit. Nanomembranes
and membrane science are veritably relevant in today’s scientific world. The
author pointedly focuses on the research endeavor in the field of both membrane
science and nanomembranes with a wide target toward the furtherance of science
and technology.
41 Nanomembranes for Environment 1035
Keywords
Nanomembranes · Environment · Sustainability · Membranes · Vision · Science
Introduction
Science and engineering of nanotechnology are surpassing visionary frontiers.

A scientist’s vision, progress of nanotechnology, and the futuristic vision of nano-
membranes are the torchbearers toward a greater scientific understanding and
a newer realm of scientific validation. Human scientific rigor is today in the midst
of immense introspection. Nanomembranes have vast and versatile applications.
Environmental engineering application is one such fundamental scientific arena.
Nanomembranes are the next largest and visionary domain of nanotechnology.
Science of nanotechnology is surpassing wide and visionary frontiers. In this
informed treatise, the author with deep introspection delineates the success of
research in the application areas of nanomembranes in environment. With immense
comprehension the author charts out a definitive and visionary future plan the
application of nanomembranes in environmental science. The challenges, the vision,
and the immediate scientific rigor need to be readdressed and reshaped at each step
of scientific advancement. Technological challenges and scientific vision are the
foundation stones of scientific research pursuit in environmental engineering today.
Membrane science and water science and water technology are the two opposite
sides of the visionary coin today. Nanotechnology and nanomembranes are changing
the face of scientific landscape today. The authors in this paper rigorously points out
the immense potential, the futuristic vision, and the vast scientific rigor of nano-
membranes in diverse applications.
Vision, Mission, and Aim of the Present Treatise
Science and technology of nanomembranes are scaling new heights and breaking
unimaginable barriers. The technology of nanomembranes is new but has immense
potential. Nanotechnology and its scientific rigor are changing the face of human
scientific progress. In a similar vein, application of nanomembranes in environmen-
tal science is witnessing drastic and dramatic challenges. The author lucidly enu-
merates with vision and challenges the success of application of nanomembranes as
a whole. Vision of science, progress of technology, and the immense importance of
nanotechnology all will lead a long way in the greater emancipation of nano-
membranes and nanoscience. A subtle scientific understanding of nanomembranes
is important toward its greater application in environmental science. The author, with
deep and cogent insight, delineates the immense potential and success of application
of nanomembranes in environmental applications. The scientific challenge, the
innovative scientific vision, and the scientific urge to move forward will veritably
propel this latent area of science toward a newer horizon.
Technological advancements are today in the state of immense revamping and

stand in the midst of scientific vision and scientific fortitude. Nanotechnology today
is surpassing vast and versatile frontiers. Membrane science and global water
research and development initiatives are changing the scientific landscape and
scientific forbearance. Scientific comprehension and scientific adjudication stand
tall and are gaining immense heights as global water challenges enter into a new era
(www.google.com; www.wikipedia.com).
Scope of the Study
Environmental engineering science is gearing for new challenges and moving

toward a newer realm of immense comprehension. The vision of science, the
scientific cognizance, and the immense scientific urge to excel will all lead a
long way in the true realization of holistic environmental sustainability. This
study brings forward to the scientific panorama the wide and latent world of
nanomembranes, its challenges, and its vast and versatile applications in environ-
mental science. The scope of the study is immense and visionary. Scientific
sagacity and the wide vision of technology are the forerunners toward the greater
scientific understanding of nanomembranes. Membranes are immensely used in
environmental engineering science. The wide and visionary world of scientific
understanding, the progress of human scientific rigor, and the civilization’s prow-
ess will all lead to a new frontier of science and engineering of nanomembranes.
The futuristic vision of application of nanomembranes should be toward its
headway into environmental engineering science. Water and wastewater treatment
in today’s resurgent human civilization are in a state of immense distress and in
unimaginable crisis. The author elegantly brings forward to the scientific horizon
the application, the definitive vision, and the future trends in research in the field of
nanomembranes. Future scope of the study and research in the field of nano-
membranes will open a new chapter in the field of nanomembranes. Vision of
science in today’s human civilization is immense, far-reaching, and surpassing
vast frontiers. At such a critical juxtaposition of science and technology, a scien-
tist’s prowess, mankind’s progress, and the scientific urge to excel will embolden
the futuristic vision of application of nanomembranes and nanotechnology as a
whole (www.google.com; www.wikipedia.com).
Introduction to the Application Area of Nanomembranes

in Environmental Applications
Science of nanomembranes is at a latent state yet a visionary domain for the future.
Human scientific challenges, scientific advancement, and scientific rigor are sur-
passing vast and versatile barriers today. Environmental engineering science is
witnessing drastic and vexing challenges. Mankind’s vision is witnessing the test
of time. The author in an informed narrative takes on the immense challenge of
Fig. 1 A nanomembrane
structure (Figure – Google
Images)
delineating the application area of nanomembranes in environmental engineering

science. Nanomembranes and its application is a domain which is part and parcel of
membrane science. Membrane separation processes and its application in environ-
mental engineering science are the hallmarks of a new visionary scientific future.
Environmental engineering disasters, the grave concern of ecological disbalance,
and the imminent vision of environmental sustainability are changing the face of
scientific research pursuit. The scientific and academic rigor of research work
in nanomembranes needs to be reenvisioned and reshaped (www.google.com;
www.wikipedia.com).
Membrane science today stands in the midst of immense scientific comprehen-
sion, scientific vision, and scientific introspection. Global water initiatives and
global water challenges are the forerunners toward a newer visionary era and a
greater emancipation of environmental engineering science today. Novel separation
processes and non-conventional environmental engineering techniques are
witnessing immense scientific rejuvenation with the sole aim of furtherance of
science and engineering of environment (Fig. 1).
Wide World of Application of Nanomembranes
Nanomembranes have numerous and wide application domain. The challenge, the
urge, and the vision of science and technology of membrane science are unimagin-
able. Human scientific understanding in the field of nanomembranes is entering a
new phase of scientific research pursuit. Drinking water treatment, industrial waste-
water treatment, and the world of environmental engineering techniques are opening
new vistas of scientific research pursuit in years to come. Membrane science and
industrial wastewater treatment today stands amidst deep scientific introspection and
the world of challenges. Global water research and development initiatives are
passing through challenging phases of scientific history and time. Global concern
for environmental protection is gaining new scientific heights. This section discusses
with deep and cogent insight the success of application of nanomembranes in various
avenues of scientific endeavor. The vision and the challenge are scientifically
awesome. Membrane science especially nanofiltration has a greater visionary avenue

of research pursuit such as desalination and water purification (www.google.com;
www.wikipedia.com).
Wastewater Treatment
Wastewater treatment is the major application domain of membrane science today.

Today the application domain of nanomembranes is veritably widening. The vision
and aim of this treatise unfold into a wider domain of nanofiltration and other
membrane separation processes. Industrial wastewater treatment is a burning and
vexing issue today. Human scientific research pursuit is challenged today. Wide
application of membrane science and nontraditional environmental engineering
techniques are witnessing drastic and dramatic changes. Application of nano-
membranes in environmental protection is the hallmark of this treatise. Wastewater
treatment, drinking water treatment, and the wide world of industrial pollution
control are the forerunners of a greater visionary eon of applied environmental
engineering science. Scientific sagacity and scientific understanding are at its helm
today with the progress of human scientific endeavor and advanced academic rigor.
Global concern for environment is the immediate need of the hour (www.google.com;
www.wikipedia.com).
Wastewater treatment, water purification, and drinking water treatment will all
lead a long and visionary way in the true emancipation and true realization of
environmental engineering science and environmental sustainability. The vision of
science, engineering science’s immense prowess, and the futuristic vision of mem-
brane science are the veritable forerunners toward a greater visionary eon in the field
of chemical process engineering and environmental science (www.google.com;
www.wikipedia.com).
Nanomembranes have immense application in wastewater treatment. There are
merits and demerits of nanomembrane technologies (e.g., nanofiltration and reverse
osmosis) over conventional filtration technologies. The conventional sand filter does
not retain some microbes and dissolved salts (e.g., arsenate). Nanofiltration (NF) and
reverse osmosis (RO) membranes remove all multivalent ions and bacteria. The
conventional carbon filter, biological sand, and biological carbon filters do not
remove some bacteria and dissolved salts (e.g., calcium). Technology of nano-
membranes is today advancing immensely faster. The vision of membrane science
is emboldened as engineering science ushers in a new era. The only additional
equipment required for NF membrane filtration, compared to conventional filtration,
is cartridge filters. One of the major setbacks of nanomembrane technology is cost.
The cost of a full-scale conventional filtration plant is about 70% of a nanomembrane
plant. Nanomembrane filtration technologies are suitable for developing countries.
Nanomembrane plants can be built as portable units, which can be assembled in the
major urban centers and then transported to the outlying areas where they are
needed. By building the plants as potable units, the initial capital required for
construction can be lowered (www.google.com; www.wikipedia.com).
Chemical Industry
Science and engineering is moving toward a newer dimension of deep scientific

cognizance. Today, scientific endeavor depends on scientific validation and the
application of science to industry. Nanomembrane is an innovative domain of
science which needs to be developed. Chemical industry and chemical engineering
domain are flourishing in today’s scientific world. Chemical process engineering in
today’s world is linked by an umbilical cord with environmental engineering sci-
ence. Nanomembranes and its application are revolutionizing the wide scientific
horizon. Human scientific endeavor and deep human introspection are rebuilding the
scientific scenario.
Nanomembrane has vast and versatile applications in chemical industry.
Scientific vision is of utmost importance in the wide path toward application of
membrane science in chemical industry and the wide world of environmental
protection. The main target areas are the manufacturing process and microscopic
structure of nanoporous ceramic membranes, mainly focusing on zeolite materials,
as well as the energy-saving effect of membrane separation expected in various
chemical synthesis process. Scientific development of separation membrane tech-
nologies that can fulfill the needs of various chemical synthetic processes is widely
envisioned (www.google.com; www.wikipedia.com).
Food Industry
Food industry is another area of science which needs deep introspection and deep
scientific optimism. Chemical process engineering and food engineering are moving
toward a newer paradigm and a newer eon of immense scientific forbearance.
Nanomembranes and its application in food industry are witnessing drastic changes
(www.google.com; www.wikipedia.com).
Food industry stands as a major target area of the application of nanomembranes.
Membrane technologies have many advantages over other separation processes in
food processing. Science and technology of membranes are witnessing paradigmatic
changes with respect to its visionary applications. Recently nanofiltration technol-
ogy, which is a very new category of membrane technology placed between reverse
osmosis and ultrafiltration, is gaining immense scientific heights (www.google.com;
www.wikipedia.com).
Biotechnology and Medical Applications
Biotechnology and biomedical engineering are the forerunners of the domain of

nanotechnology today. Vision of science, the world of scientific challenges, and the
wide road toward scientific progress are today leading a long way in the true
emancipation and realization of environmental sustainability, environmental engi-
neering science, and biotechnology. Biotechnological science is revolutionizing and
a vapor/liquid deposition b self-assembled c electron-irradiation d free-standing

monolayer induced crosslinking nanomembrane
(i) (ii) (iii)
adsorption e– / hν dissolving
vdW interactions substrate
Fig. 2 Fabrication of nanomembrane (Figure – Google Images)
restructuring the wide scientific horizon. A scientist’s prowess, mankind’s deep

introspection, and man’s vision are the forerunners toward a greater visionary era
of science (www.google.com; www.wikipedia.com).
Fabrication and Mechanism of Separation in Nanomembranes
Fabrication and mechanism of separation phenomenon in the area of nano-

membranes are the definitive hallmarks of environmental engineering science
today. The success of separation phenomenon has changed the face of scientific
rigor today. The art of fabrication and the knowledge of separation in nano-
membranes are of utmost importance in today’s world of chemical process engi-
neering and environmental engineering science. The question of effectiveness of
separation processes needs to be addressed in each step of scientific rigor of
nanomembranes (www.google.com; www.wikipedia.com) (Fig. 2).
Science, Human Mankind, and the World of Environmental

Sustainability
Technology and engineering science are moving at a rapid pace in our present-day
human civilization. Sustainable development and energy and environmental sustain-
ability are the coin words of today. Technology and science of environmental
protection are advancing at a veritably rapid pace. Scientific vision, scientific
rejuvenation, and scientific profundity will lead a long and visionary way in the
true emancipation of environmental science today. Environmental protection and
environmental sustainability are the two opposite sides of the visionary coin today.
The challenge and the vision of sustainability need to be rebuilt and revamped with
the passage of scientific history and time. Mankind and environmental protection
today stand in the midst of deep distress and untold catastrophe. The challenge and
vision of environmental sustainability in such a situation need a scientific over-
hauling. Novel separation processes and non-conventional environmental engineer-
ing techniques such as advanced oxidation processes are gaining immense heights
today. Scientific pinnacles and scientific profundity have no veritable ends in the
path of science today. Membrane separation science is one of the many achievements
of science and engineering today. Human society and human scientific endeavor
need to attain rigorous scientific and academic rigor in such a crucial juncture
of history and time. In this treatise the author widely observes the success of
mankind’s advancement with respect to energy and environmental sustainability.
Nanomembranes are the wide vision of science today. Diverse applications,
immense potential, and the futuristic vision are the technology drivers of nano-
membranes and membrane science today. Water purification, industrial wastewater
treatment, and the vast vision of membrane separation processes are the veritable
backbones of this study. Environmental engineering science today stands in the
midst of deep comprehension and scientific introspection. The author treads a
visionary path in the search of real scientific truth.
Today the breach in sustainability issues by developed and developing countries
stands as an immense disdain to the future of human civilization and for the
furtherance of science and technology. Global water issues and the burning and
vexing issue of groundwater heavy metal contamination are changing the scientific
mindset of the present scientific generation. This treatise widely observes with deep
foresight the success of membrane science and the application of nanomembranes in
solving the enigma of water pollution control and water purification. Sustainability
issues and related scientific forays should in the present-day human civilization
target toward the betterment of human society and the advancement of science and
technology.
Nanotechnology, Sustainability, and the Vision for the Future
Nanotechnology is a visionary and far-reaching avenue of scientific endeavor today.

Diverse innovations in various branches of nanoscience and nanotechnology are
ushering in a new eon of scientific rejuvenation. The challenge and the vision for the
future are wide, well researched, and groundbreaking. Sustainability and the appli-
cation of nanotechnology are the forerunners of advancement of science today.
Nanotechnology, drinking water treatment, and the wide world of membrane sci-
ence/nanofiltration are leading human civilization toward a greater emancipation of
environmental engineering science and chemical process technology. Nanofiltration
and groundwater remediation are the technology drivers of global water research and
development initiatives. Technological emancipation and its profundity are changing
the face of human civilization today. Arsenic and other heavy metal groundwater
contamination are being challenged with the passage of scientific history and
scientific cognizance. The author in this treatise profoundly discusses the deep vision
of nanofiltration and nanotechnology for water purification and industrial wastewa-
ter treatment. The author demonstrates with deep conscience the case of examination
of a developing country’s inroads into groundwater quality management (example
of India). Groundwater concerns, the wide scientific prowess of heavy metal
remediation, and the vast scientific rigor are all leading a long and visionary way
in the true realization of environmental engineering paradigm (www.google.com;
www.wikipedia.com).
Scientific Research Pursuit in the Field of Nanomembranes
Science and technology in today’s scientific horizon are moving at a rapid pace. The
author in this section repeatedly points out the immense potential, the wide success,
and the visionary future of nanomembranes. Membrane science and chemical
process engineering are crossing visionary frontiers of scientific vision today.
Today progress of human civilization depends upon the provision of basic human
needs and the greater emancipation of water science and technology. Groundwater
contamination issues and the success of global water research and development
initiatives are changing the face of human scientific endeavor. Nanomembranes and
the wide world of membrane science are gearing toward a newer paradigm in years
to come. This treatise widely observes the immense potential, the vast and varied
scientific success, and the future trends in research in the field of membrane science.
Kumar et al. (2014) reviewed nanomembrane and its vast and versatile applica-
tions. The nanomembrane plays an important role in diverse fields of human
scientific endeavor. Its applications such as cylindrical-, conical-, and pyramidal-
shape pores are the wide avenues of scientific research pursuit. Surface modification
of nano-pore size surfaces can give unique mass properties and characteristics that
have recently explored for polymers, fibers, and biomolecule separation, detection,
and purification. In this widely observed treatise, the targeted focus will be toward
the use of nanomembrane for mass transfer diodes that can act analogous to solid-
state devices based on electrical conduction. Other applications of nanomembranes
are the area of nanopolymers for separation of biomolecules, biosensing, micro-
fluidics, logic gates, and the visionary area of energy harvesting and storage.
Nanomembranes may be defined as synthetic structures with a thickness below
100 nm and surface-area-to-volume ratio increase aspect of at least a few orders of
magnitude. Technological vision and scientific objectives are enhanced as mankind
treads a visionary path in the field of nanotechnology and the wide area of nano-
membranes. Being quasi-2D, they exhibit a host of unusual properties useful for
various applications in energy harvesting, sensing, optics, plasmonics, biomedicine,
etc. Molecules designed at the nanometer scale using membranes like polymers offer
greater potential for high selectivity and high fluxes.
Jaksic et al. (Jaksic and Matovic 2010) reviewed functionalization of artificial
freestanding composite nanomembranes. Artificial nanomembranes may be defined
and envisioned as synthetic freestanding structures with a thickness below 100 nm
and a very large aspect ratio of at least a few orders of magnitude. Being quasi-2D,
they exhibit a host of unusual properties useful for various applications in energy
harvesting, sensing, optics, plasmonics, biomedicine, etc. Technology is so much
challenged today and needs to be reenvisioned and re-envisaged with the passage of
scientific history and vision. Environmental protection science stands in the midst of
immense distress and deep crisis. The authors reviewed the main approaches to
nanomembrane functionalization through nanocompositing, which ensures perfor-
mance far superior to that of simple nanomembranes.
Choi et al. (2007) delineated with cogent insight biaxially stretchable “wavy”
silicon nanomembranes. Technological vision and scientific motivation in the field
of nanomembranes are paving the path toward a newer visionary era in the field of
environmental engineering science. This treatise introduces a biaxially stretchable
form of single-crystalline silicon that consists of two dimensionally buckled,
or “wavy,” silicon nanomembranes on elastomeric supports. The wide vision of
membrane science and nanofiltration technologies is opening up new dimensions
in global research and development initiatives in water science and technology.
Fabrication procedures for these structures are described, and various aspects of
their geometries and responses to uniaxial and biaxial strains along various direc-
tions are presented. Technology of nanotechnology is moving very fast in a positive
future direction. Human scientific endeavor and scientific rigor are changing the
wide face of human civilization’s progress. This treatise goes into the details and
intricacies of nanomembranes with a veritable success toward the furtherance of
science and engineering. Materials engineering and materials science are opening up
new avenues of scientific research and deep scientific understanding.
Matovic et al. (Matovic and Jaksic 2009) discussed lucidly nanomembranes as a
new MEMS/NEMS building block. Technology of nanomembranes is highly
advanced today and is surpassing wide and vast scientific frontiers. Although
MEMS devices are exceptionally diversified, all of them are basically built from a
limited number of constituents manufactured in micrometer-size dimensions: plates,
cantilevers, bridges, and channels. It is this foundation of these basic building blocks
that makes the almost limitless variety of MEMS devices. The science and technol-
ogy of nanomembranes today are linked with wide variety of applications such as
membrane science and water treatment. Engineering science of membrane separa-
tion techniques are opening up new windows of immense innovation in the field of
global water research and development initiatives. This paper gives the readers the
fundamental aspects of nanomembrane applications with the sole aim of furtherance
of scientific vision and scientific understanding.
Yang et al. (2015) delineated with deep scientific insight transfer-printed nano-
membranes for heterogeneously integrated membrane photonics. This is a vast area
of scientific endeavor. Heterogeneous crystalline semiconductor nanomembrane
(NM) integration is investigated for single-layer and double-layer silicon photonics,
silicon nanomembrane lasers, and graphene/Si nanomembrane total absorption
devices. Both heterogeneous and homogeneous integration are realized by the
versatile transfer printing technique. The performance of these integrated membrane
devices shows not only intact optical and electrical characteristics as their bulk
counterparts but also the unique light and matter interactions. This paper gives a
fundamental idea of the application of nanomembranes and opens up a new chapter
in the field of applied physics.
Markutsya et al. (2005) discussed with lucid details freely suspended layer-by-
layer nanomembranes with the main objective of testing micromechanical proper-
ties. Freely suspended nanocomposite layer-by-layer nanomembranes composed of
a central layer of gold nanoparticles sandwiched between polyelectrolyte multilayers
are fabricated via spin-assisted layer-by-layer assembly. The diameter of the circular
membrane is varied from 150–600 μm, and the thickness is kept within the range of
25–70 nm. Nanomembranes are opening a new chapter of scientific regeneration and
deep scientific vision. This paper gives a wider knowledge of nanomembrane

fundamentals with the sole aim of expanding the scientific vision and scientific
cognizance.
Rogers et al. (2011) reviewed synthesis, assembly, and application of semicon-
ductor nanomembranes. Research on electronic nanomaterials, totally dominated by
studies of nanocrystals/fullerenes and nanowires/nanotubes, now encompasses a
growing focus on sheets with nanoscale thicknesses, referred to as nanomembranes.
Engineering science of nanomembranes is widely advanced and crossing visionary
scientific boundaries. In this paper, the authors deeply focus on the immense
potential and the success of application of this widely innovative material. Such
materials have practical appeal because of their two-dimensional geometries that
facilitate integration into devices. Material science and nanomaterial science are
opening up new avenues of scientific thoughts and scientific avenues in years to
come.
Carbon Nanotube-Based Membranes for Environment
Carbon nanotube-based membrane is the next-generation membrane technology.

Environmental engineering science is opening up new avenues of scientific and
academic rigor in the decades to come. The vision of science is purposeful and
definitive. The author deeply comprehends the vision, the challenge, and the
success of the application of nanomembranes in environmental engineering sci-
ence. Global water issue is witnessing unimaginable environmental disasters
mainly arsenic and heavy metal groundwater contamination. Global water short-
age is a burning and vexing issue which needs to be reenvisioned at every step of
human civilization. Diversification of membrane technology and innovation in the
domain of nanomembranes are the veritable solution for the future. A scientist’s
improved vision, mankind’s prowess, and the futuristic road to excel in science are
the hallmarks of a newer scientific generation in the field of nanotechnology and
nanomembranes.
Nano-biomembranes and Environmental Monitoring
Environmental monitoring stands as a major component in scientific excellence

and scientific cognizance in the field of environmental engineering science. Grave
concern for environment, catastrophes of environment, and the recurrent environ-
mental engineering disasters are leading a long and visionary way in the true
realization of environmental sustainability. Nano-biomembranes and its applica-
tions are touching new scientific heights. Environmental monitoring is the back-
bone of the greater realization of environmental engineering science in today’s
world. Human scientific rigor, the scientific urge to excel, and the futuristic vision
of tomorrow will all lead a long way in the true emancipation of environmental
engineering science.
Nanocomposite Membranes for Environment
Nanocomposite membranes are reshaping the future of membrane science.

Technological vision and scientific and academic rigor in the field of nanocomposite
membranes are scaling visionary heights. Environmental science is today in the
midst of immense introspection. The challenge of science, the immense scientific
rigor, and the advancements of science and technology are the veritable landmarks
toward a greater realization of environmental engineering tools. In this world of
challenges and scientific fortitude, scientific validation evokes immense importance.
The frontiers of science, the fruits of engineering, and the progress of technology are
gearing for newer challenges and drastic vision. Membrane science and its intricate
separation phenomenon are changing the face of advancement of science.
Polymer Nanomembranes for Environment
Polymer nanomembranes and its application in environment are the next biggest and
visionary challenge in the vast world of scientific research pursuit in membrane
science. A scientist’s immense prowess, the achievements of science, and mankind’s
definite vision are the pallbearers of tomorrow’s environmental engineering tech-
niques. Environment needs to be free of the difficulties and barriers of scientific
advancement. In such a crucial juxtaposition, polymer nanomembranes and its
scientific advancement are crossing visionary heights.
The Future of Nanomembranes
The challenges, the concern, and the scientific vision behind the application of
nanomembranes in environmental are vast and versatile. Human scientific endeavor
and the world of scientific rigor are witnessing toughest and vicious challenges.
Membrane science and membrane separation phenomenon are in the path of
immense scientific rejuvenation and scientific candor. Environmental disasters, the
grave concern for ecological disbalance, and the urge for human scientific excellence
will all lead a long and visionary way in the true realization of membrane separation
phenomenon. Research pursuit in today’s world is faced with ever-growing chal-
lenges. Future of application of nanomembranes is in a state of immense optimism
and hope. Science, technology, and engineering of membrane science are in the path
of newer glory and a newer visionary realm. Thus, in such a critical juncture of
human history and time, protection of environment and the evolution of new
environmental engineering techniques will change the face of scientific vision in
today’s human civilization.
Vision of science and engineering is gearing toward a newer direction.
Environmental engineering science and scientific research pursuit in the field of
environmental sustainability are progressing toward new future trends and a futur-
istic scientific horizon. The progress of mankind and the state of environment is at
a deep distress. Membrane science, nanomembranes, and successful application

of membrane technology are changing the scenario of global water shortage.
The futuristic trends of nanomembranes stand today as the only definite answer.
The future of membrane science is wide and versatile. Technology today is vastly
advancing. The vast progeny of science, the scientific profundity, and the cause of
environmental protection will veritably go a long and visionary way in the ushering
in of a new era in the field of environmental engineering science.
Vision of Nanotechnology in the Treatment of Wastewater
Nanotechnology is a visionary technology for the future. Wastewater treatment and

water treatment in today’s scientific horizon stand in the midst of deep scientific
vision and wide scientific understanding. Membrane separation processes are chang-
ing the scientific scenario of research pursuit. The vision of nanotechnological
methodology and nanoscience is uncovering the wide latent world of nano-
membranes. Wastewater treatment and drinking water treatment are of immense
and vital importance in the future progress of human scientific endeavor. The vision
and the challenge of human civilization and scientific endeavor are surpassing wide
boundaries.
Nanotechnology is surpassing all visionary boundaries today. Mankind’s techno-
logical prowess is at a state of deep distress as environmental protection gears up for
newer challenges. Industrial wastewater treatment is in a state of immense scientific
introspection today. Nanomembrane science is invariably linked with the advance-
ments in membrane science and water purification. Technology of water purification
and drinking water treatment needs to be steadfast with the passage of scientific
history and time. Nanotechnology in the similar vein needs to be revamped as
nanomembrane gains newer and visionary heights.
Water Pollution and Nanofiltration
The science of membrane science and the relevant field of nanofiltration are sur-
passing wide and vast visionary frontiers. Environmental concerns, grave causes of
ecological disbalance, and scientific validation of academic rigor are the forerunners
of greater emancipation of environmental engineering science today. The other side
of the environmental engineering coin is the suitability of environmental degradation
techniques. Global water challenges are changing the face of scientific and academic
rigor in environmental science and chemical process engineering. Heavy metal
groundwater contamination is changing the scientific horizon of global environmen-
tal engineering science. Developed and developing economies throughout the world
are in the veritable stronghold of groundwater and drinking water contamination.
The evolution of environmental engineering techniques and novel separation pro-
cesses are the pallbearers toward a greater realization and effective attainment of
environmental sustainability. Industrial water pollution and contamination of pure
drinking water is a bane to human civilization. This treatise broadly focuses on the
evolution of nanomembranes as an effective tool toward environmental pollution
control. Human civilization’s progress and the concern for environment are at a
difficult state of affairs today. Proper provision of clean drinking water is a massive
failure of human civilization and human scientific endeavor. Nanomembranes and its
wide application to environment are the most effective innovations of this century.
Water is the most important item to human holistic growth. Yet the global water
crisis is a bane to human scientific progress. The challenge of human civil society
needs to be reenvisioned at each step of scientific advancements and scientific
progress in industrial pollution control. Water plays a significant role in the world
economy, as it functions as a solvent for a wide variety of chemical substances and
envisions industrial cooling and heating operations. Exclusively to people in devel-
oping countries as well as some of developed countries, scarcity of water, in terms of
both quantity and quality, poses a monstrous threat to the current and future well-
being of people worldwide.
Sustainable water management and integrated groundwater quality management
are crucial aspects of addressing poverty, equity, and related issues. In such a critical
juncture, science and technology has a wide and visionary role to play in contribut-
ing to the development of new systems, tools, and techniques to solve specific water
quality and quantity issues. Nanofiltration is a classification and a branch of mem-
brane science. Immense scientific potential of membrane science and the compre-
hensive scientific vision of nanofiltration are leading a long and visionary way in true
realization of global industrial pollution control. The concept of nanofiltration and
other membrane separation processes is veritably changing the global environmental
engineering scenario. The author deeply comprehends the tremendous potential and
the latent acumen of nanofiltration as an environmental engineering technique.
Human scientific challenges are immense with the grave concern for environment.
This treatise greatly discusses the success of application of nanofiltration in indus-
trial water pollution control.
Shannon et al. (2008) discussed with deep and cogent insight science and
technology for water purification in the coming decades. One of the most important
problems afflicting people throughout the world is inadequate access to clean
drinking water and proper sanitation. Problems with water are expected to grow
worse in the coming decades, with water shortage occurring globally, even in regions
which are water-rich. To address such a problem, tremendous amount of research
needs to be reenvisioned with the passage of scientific endeavor.
Desalination, Future of Water Science, and the Wide Progress

of Nanomembranes
Global water shortage is a bane to human civilization and detrimental to the holistic
human scientific endeavor. Seawater desalination is veritably alleviating the global
water crisis. The technology of desalination and water treatment needs to be
reenvisioned. The scientific advancements in the field of membrane separation
processes are witnessing drastic and effective challenges. The challenge of science
and technology is widening and also surpassing visionary boundaries. Scarcity of
safe drinking water has urged the global scientific community to gear toward newer
technologies and innovative global water initiatives. Novel separation techniques
and nontraditional environmental engineering techniques are changing the face of
human academic endeavor. Here comes the issue of arsenic and heavy metal
groundwater contamination. Today application of nanomembranes and membrane
technology is witnessing a world of devious scientific challenges. The wide progress
of nanomembranes and the application of membrane science have a scientific
umbilical cord which is paving the long and visionary way of successful environ-
mental engineering techniques. Holistic sustainable development needs to be rebuilt
and restructured with each step of scientific endeavor of desalination science. The
difficulties and barriers of advanced scientific endeavor in membrane science and
desalination science are uncovering the scientific truth and scientific understanding
with immense potential. Chemical process engineering and the world of chemical
process design are the veritable forerunners toward the application of membrane
technology and desalination technique (Hashim et al. 2011).
Water science and technology, membrane science, and desalination technology
are today surpassing wide and vast visionary frontiers. Novel separation processes
are the torchbearers toward a greater visionary eon in separation phenomenon today
(Hashim et al. 2011).
Suitability of the Nanomembrane Technologies
Human civilization and human scientific rigor are moving toward a newer era of
nanomembrane technologies. The challenge and vision of science are unfolding the
murky depths of nanomembrane science and membrane technology as a whole.
There are worldwide merits and demerits of nanomembrane technologies (e.g.,
nanofiltration and reverse osmosis) over conventional membrane technologies.
The conventional sand filter does not retain some microbes and dissolved salts
(e.g., arsenate). Nanofiltration (NF) and reverse osmosis (RO) membranes remove
all multivalent ions and bacteria. Conventional carbon filter and other biological
sand filters do not remove some bacteria and dissolved salts (e.g., calcium). Calcium
is readily removed by the membrane processes.
The only other additional equipment required for NF membrane filtration, com-
pared to conventional filtration, is cartridge filter. These serve as a pretreatment for
the removal of particulate matter before membrane filtration. Their cost is insignif-
icant. One of the setbacks of membrane technology is cost.
Nanomembrane technologies are changing the face of scientific and academic
rigor in the field of membrane science. Nanotechnology is opening up new vistas in
the domain of nanofiltration, reverse osmosis, and wide application area of nano-
membranes. The vision and challenge of nanotechnology are the forerunners toward
a newer innovative era of environmental engineering science. The author repeatedly
focuses on the success of nanomembranes and the wide world of nanofiltration

application in environmental pollution control. Human scientific endeavor needs to
be reenvisioned with the march of nanotechnology.
Nanofiltration Membranes
Human scientific endeavor in today’s scientific and technological horizon stands in

the midst of immense optimism and deep introspection. Nanofiltration is a classifi-
cation of membrane science. Industrial water pollution control is the utmost need of
the hour. The challenge of human civilization and subsequent scientific endeavor
needs to be reenvisioned at each step of human life. Water crisis is an overwhelming
phenomenon which is drastically devastating the scientific fabric and technological
horizon in years to come. Mankind’s prowess and civilization’s wide avenue of
progress today are immensely retrogressive. In today’s visionary era, nanofiltration/
membrane science is linked by an umbilical cord with global water challenges and
the science of desalination.
Global water disaster and the unending calamities associated with it are urging the
scientific domain and the human civil society to yearn for new innovations and
groundbreaking techniques. Scientific challenges, scientific rigor, and the efficacy of
nanofiltration/membrane science are the torchbearers toward a greater visionary
decade in the field of global water challenge. The application areas of nanofiltration
are widening. Science has few answers to the widening crisis of global water
shortage. Chemical process engineering, chemical process modeling, and the wide
and visionary area of environmental engineering science are changing the scientific
paradigm of tomorrow (Shannon et al. 2008; Hashim et al. 2011; Gilmour 2012;
Goi 2005).
Nanocatalysts and Magnetic Nanoparticles
Nanocatalysts are the next-generation innovative technology and next-generation

materials. Science of nanocatalysts is unfolding new chapter in the wide visionary
domain of nanotechnology. Magnetic nanoparticles are veritably opening up new
vistas of scientific research and scientific vision. The challenge of human civilization
is awesome and groundbreaking. Nanocatalysts are particles with catalytic proper-
ties that can chemically break down pollutants. Their wide use mitigates the exten-
sive cost of transporting them elsewhere. This, in turn, has the potential for treating
contaminants at very low levels, especially where the current treatment techniques
are ineffective or very expensive. The vision of the application of nanocatalysts is
immense and far-reaching. The main positive function of nanocatalysts is their
ability to bind with contaminants, such as arsenic or oil, which can be easily removed
using a magnet, making them an appealing solution for water treatment and indus-
trial wastewater treatment.
Vision Behind Sensing and Detection
Nanotechnology is being used to develop small and portable sensors with enhanced
capabilities for detecting biological and chemical contaminants at very low concen-
tration levels in the environment, including in water. The science and vision of
nanomembranes are opening up new chapters in the field of nanoscience and
nanotechnology.
Increasing Potable Water Supplies
The development of low-cost portable filters, purifiers, and other techniques could
positively impact rural areas and informal settlements located close to industrial
areas, where drinking water is highly contaminated. Industrial pollution control in
today’s world stands in the midst of deep crisis. Drinking water treatment should be
readdressed at each step of human life. The strong human conscience and scientific
cognizance will lead a long and visionary way in clear understanding of the
difficulties and barriers of drinking water treatment. The challenge of science and
engineering needs to be redrawn.
Desalination of Seawater and the Vast Future of Science
Desalination is another vibrant avenue of environmental engineering science. By

removing the salt from seawater, another large sustainable source of potable water
needs to be reenvisioned. Environmental protection is a visionary avenue of scien-
tific endeavor. The challenge and vision of science and technology of desalination
are gaining new grounds. Human civilization is moving from one paradigm toward
another. The growing concern for groundwater contamination and the success of
integrated groundwater quality management have urged the scientific domain to
devise newer environmental engineering techniques such as novel separation pro-
cesses and advanced oxidation techniques. Desalination technique is the only feasi-
ble solution in the provision of clean drinking water. The challenge, the vision, and
the mission of human society and the civil society should be toward the effective
global water solutions.
Safety of Industrial Effluent
Safety of industrial effluent is of growing concern. The protection of environment

should go alongside safe industrial practices. Human scientific endeavor and scien-
tific progress are moving toward a newer millennium. In such a crucial juncture
of human history and time, chemical process safety is of utmost importance.
Nanotechnology may be used by the mining industry to prevent the contamination
of groundwater from inactive mines by cleaning of acid mine drainage sources.
Benefits of Nanotechnology and the Scientific Vision

and Scientific Comprehension
Nanotechnology is today a revolutionary avenue of science. The forerunners of the

concept of nanotechnology are increased effectiveness, removal of new contami-
nants, simplification, and reduced cost. The challenge of nanoscience and nanotech-
nology is unimaginable. Deep scientific vision and unmitigated environmental
disasters are changing the scientific landscape of the application domain of nano-
technology. Contaminants could be more effectively removed, even at low concen-
trations, and the development of “smart” filters needs to be envisioned.
Contaminants that were previously impossible to remove could now be removed.
The technique should be simplified. Nanotechnology could drastically reduce the
number of steps, materials, and energy needed to purify water, making it easier to
implement in wider domains.
Regulation of Nanotechnology
At present, there are no nanotechnology-specific regulations in many nations mainly

due to the relative infancy of the present technologies. Another side of the coin is the
lack of evidence and scientific validation to support the application of the technology
and the impact of the products. It is imperative that nanotechnology should be
developed in a safe, responsible, acceptable, and sustainable way. Technology
development should be sustainable. Sustainability, whether it is energy or environ-
mental, should gear toward a newer visionary era. Scientific challenges, the scientific
urge to move forward, and the immense potential of nanoscience and nanotechnol-
ogy are all gearing toward a newer eon in decades to come.
Scientific Validation and Technology Transfer
Developed water science and water technologies need to be transferred to specific

target communities and must be relevant to the society’s needs, technological
capability, and available infrastructure. Human needs should be linked to nanotech-
nology today. The challenge of technology and engineering will veritably unfold
toward a newer beginning in nanotechnology. Scientific validation and technology
transfer are extremely necessary in today’s scientific world. Nanotechnology and
nanomembranes are today revolutionizing the scientific landscape. Technology
transfer and scientific validation are the cornerstones of research today. The progress
of scientific endeavor, the immense scientific and academic rigor, and the challenge
of science and engineering are veritably leading toward newer emancipation of
environmental engineering and relevant areas of nanotechnology (Hashim
et al. 2011).
Nanotechnology and nanoengineering are today ushering in a new era of scien-
tific regeneration and technological profundity. Membrane science and
nanomembranes today are challenging and enigmatic areas of scientific endeavor.

The success of scientific progress and the immense concern of sustainable develop-
ment are changing the vast and versatile landscape of nanotechnology. Nanotech-
nology is reframing the world of science and engineering today (Hashim et al. 2011).
Nanotechnology Risk Assessment
Long-term acceptance of nanotechnology-based products and industrial applications

by society is strongly dependent on the way risk concerns will be effectively
investigated and communicated to the public. The challenge of human civilization
needs to be reenvisioned at each step of human scientific endeavor. Nanotechnology
risk assessment is the need of the hour. The scientific urge in the application of
nanotechnology techniques needs to be rebuilt with the reference to risk assessment.
Risk assessment is a futuristic coin word and is of utmost importance in the progress
of science and technology. The challenge and the vision of nanotechnology risk
assessment are far-reaching and ever-growing. Nanotechnology is a visionary
domain of scientific research pursuit today. The technology is groundbreaking yet
latent. In this treatise the author treads a visionary path in the field of nanotechnology
and membrane science. The vision forward in the advancement of science is
changing the scientific landscape. Scientific rigor of chemical process engineering,
the futuristic vision of nanotechnology, and the scientific risks behind application of
nanotechnology are all leading a long way in the true emancipation and true
realization of nanomembranes today. The windows of innovation and the doors of
scientific instinct are wide open as human civilization and scientific endeavor usher
in a new era.
Technology Validation, Scientific Introspection, and Vision

for the Future in Nanomembranes
Technological validation and deep scientific introspection are the cornerstones of the
future scientific endeavor in the field of nanomembranes. Environment today stands
in the midst of veritable crisis. Industrial pollution control and water purification are
gaining new heights as science and engineering moves from one visionary paradigm
to another. Scientific introspection and deep scientific comprehension are the fore-
runners and the torchbearers toward a greater realization of membrane science and
environmental engineering science today. Scientific and technological validation are
the immense necessities of scientific research pursuit today. The immense scientific
prowess, the wide potential of engineering science, and the barriers of application of
science are opening up new windows of scientific innovation in years to come.
Nanomembranes and membrane science are the two opposite sides of the visionary
coin today. Science today is a huge colossus without a definite will of its own with
the immense concerns for environmental disasters, loss of ecological biodiversity,

and the growing nuclear proliferation. In such a crucial juncture, scientific and
technological validation will lead a long and visionary way toward the scientific
vision and scientific truth.
Environmental Sustainability, Application of Membrane Science,

and the Wide World of Nanomembranes
Sustainable development is in the path of newer scientific regeneration and a newer

avenue of scientific forbearance. Membrane science applications, the world of
challenges in groundwater remediation, and the success of scientific and technolog-
ical validation are the torchbearers toward a wider emancipation of environmental
engineering science today. Mankind’s immense scientific rigor, science’s vast poten-
tial, and technological and engineering progress are veritably transforming the fruits
of scientific research pursuit. Sustainable development, whether it is energy or
environment, is surpassing visionary boundaries. Scientific fervor, technological
splendor, and the world of challenges in science are all leading a visionary and
definite way in the true realization of environmental sustainability. Membrane
science and global water research and development initiatives are today linked by
an unsevered umbilical cord. Desalination science is another visionary avenue of
scientific research pursuit today. This treatise widely observes the success of mem-
brane science in solving global water issues.
The Challenge and True Vision of Environmental Engineering

Separation Processes
The true challenge and vision of environmental engineering separation processes are
paving the path toward newer scientific vision and scientific forbearance. Membrane
separation phenomenon and global water challenges are the vexing and enigmatic
areas of scientific endeavor today. Technological challenges and technological
profundity in the field of environmental engineering separation processes are today
linked to global water issues and global water challenges. This treatise also pointedly
focuses on the success of environmental engineering techniques such as advanced
oxidation processes and membrane separation processes. This area needs to be
explored and reenvisioned. Environmental engineering separation processes
and chemical process engineering are redefining the embodiment of science. The
futuristic endeavor and the challenge are enormous and surpassing wide barriers.
Separation phenomenon, the world of industrial wastewater treatment, and water
purification are all leading a long way in the true realization of environmental
engineering science today. Global climate change issues, loss of ecological balance,
and the success of environmental sustainability are the torchbearers toward a greater
visionary eon in the field of environmental engineering science.
Nontraditional Environmental Engineering Techniques

and Membrane Science
Nontraditional environmental engineering techniques such as advanced oxidation

processes are other backbones and cornerstones of this study. The author repeatedly
focuses on the scientific success, scientific rejuvenation, and scientific candor in the
field of advanced oxidation processes. Ozonation and its varied applications are
the other wide backbones of this study. Human scientific endeavor and vast and
versatile research pursuit are truly changing the scientific and technological horizon.
Sustainability and holistic sustainable development are the focal points of this
widely observed treatise.
Nontraditional environmental engineering tools such as advanced oxidation
processes are changing today’s scientific landscape. Ozone oxidation or ozonation
is the groundbreaking avenue of science and engineering today. Scientific vision,
scientific cognizance, and scientific understanding are all leading a long way in the
true realization of environmental engineering science today (Cheryan 1998; Palit
2015, 2016).
The Challenge and Vision of Scientific Validation
Scientific validation and technology profundity in the field of membrane science

applications are the immediate need of the hour. Environmental engineering science
and scientific ingenuity are in the path of new scientific rejuvenation today. Chemical
process engineering and the larger world of membrane separation processes are
challenging the field of science and engineering. Global water initiatives and provi-
sion of clean drinking water are the true parameters of scientific progress and the
progress of human civilization. Scientific validation, technological vision, and
motivation are of utmost importance in the future endeavor of science (Cheryan
1998; Palit 2015, 2016).
Scientific and technological validation are in the path of newer scientific
rejuvenation in the present century. Nanomembranes and membrane science
are today revolutionizing the path of scientific vision. The vast challenges of
engineering science, the global water issues, and the ever-growing concerns of
drinking water contamination are all leading a long way in the true emancipation
of sustainable development today. Environmental and energy sustainability are the
torchbearers toward a newer age of scientific vision today. Technological motiva-
tion and scientific objectives are the foundation stones of scientific endeavor in
today’s human civilization. Global water challenges and global water research and
development initiatives are reframing the holistic domain of environmental sus-
tainability. In this treatise, the author rigorously focuses on the success of appli-
cation of nanomembranes in environmental protection with the stringent and sole
aim toward true realization of environmental sustainability (Cheryan 1998; Palit
2015, 2016).
Future Environmental Perspectives and Vision of Application of

Nanomembranes
Future trends in membrane science research and future environmental perspectives

are in the path of newer scientific regeneration. In today’s world, science
and engineering are colossus with a definite vision of its own. The perspectives
of science are inspiring and crossing wide and vast visionary boundaries.
Nanomembrane science and nanomembrane research are today in the crossroads
of human scientific vision and deep scientific cognizance. Global water issues and
global water challenges are changing the face of science today. Drinking water
treatment, industrial wastewater treatment, and the far-reaching avenues of environ-
mental engineering science are the pallbearers toward a visionary era in the field of
environmental protection today (Cheryan 1998; Palit 2015, 2016).
Future Dimensions and Future Trends in the Application of

Nanomembranes
Future trends in the research domain of application of nanomembranes are wide,

groundbreaking, and surpassing unimaginable scientific frontiers. The greatness and
glory of science in the application of nanomembranes in today’s scientific world is
scaling new heights. Scientific rejuvenation, the glory of science, and the future road
toward progress are the hallmark toward newer scientific frontiers. Nanomembranes
and its application are the next-generation science and engineering. The grave
concerns of ecological disbalance are changing the face of environmental engineer-
ing separation processes and novel separation phenomenon. Vision of science and
the progress of engineering are witnessing the toughest times in our present-day
human civilization (Cheryan 1998; Palit 2015, 2016).
The challenge, the progress of human scientific rigor, and the fruits of technology
and engineering are the torchbearers toward a greater scientific understanding of
membrane separation phenomenon in years to come. The futuristic vision of the
domain of membrane science is inspiring as well as groundbreaking. Science and
engineering has a purposeful vision of its own. Nanomembranes and its applications
will surely open up new vistas of research in decades to come. The challenge of
future and the barriers and difficulties need to be reenvisioned with every step of
human scientific rigor (Cheryan 1998; Palit 2015, 2016).
Summary and Conclusion
Membrane separation processes in today’s scientific genre are facing the toughest
challenges of our times. Global water crisis and global water shortage are in the path
of unimaginable disaster. Science and technology has a definite vision of its own.
The immediate vision of science is to alleviate the disaster of global water crisis and
groundwater contamination. In such a crucial situation of human history and time,
provision of basic human needs is of utmost importance. Technology of membrane

separation processes is moving at a rapid pace. Human scientific rigor in alleviating
global water crisis and sound realization of environmental engineering tools are the
immediate need of the hour. Nanomembrane research endeavor will definitely go a
long way in solving global water issues. The paradigm of the domain of nano-
membranes stands tall in the scientific horizon. Human society’s progress and the
vision of science and technology will surely be the hallmarks of future human
civilization. Nanomembranes and membrane separation processes will definitely
surpass frontiers of science. The burning and vexing question of global water
shortage is opening up new vistas in research of membrane separation processes
and the area of nanomembranes. The world of challenges will surely be successful as
human civilization enters into a new phase of environmental sustainability and true
realization of membrane separation processes.
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Exergy and Life Cycle-Based Analysis
42
Niloufar Salehi, Morteza Mahmoudi, Alireza Bazargan, and
Gordon McKay
Contents
Exergy Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
Basic Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1059
Exergy Efficiencies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060
Strengths and Limitations of Exergy Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1061
LCA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1062
History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1062
LCA Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1064
Goal and Scope Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1064
Inventory Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1065
Impact Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1065
Interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1067
Iterative Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1067
Strength and Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1067
Limitations of LCA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1068
Exergy-Based Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1069
Exergetic Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1069
Exergoeconomic Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1071
Exergoenvironmental Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1074
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1077
N. Salehi · M. Mahmoudi
Energy Research Institute, Sharif University of Technology, Tehran, Iran
A. Bazargan (*)
Department of Civil Engineering, K.N. Toosi University of Technology, Tehran, Iran
e-mail: alirezabazargan@kntu.ac.ir
G. McKay
Division of Sustainable Development, College of Science and Engineering, Hamad Bin Khalifa
University, Qatar Foundation, Doha, Qatar
e-mail: gmckay@hbku.edu.qa

https://doi.org/10.1007/978-3-319-73645-7_84
1058 N. Salehi et al.
Abstract
The concept of exergy, defined as “the maximum useful work which can be
extracted from a system as it reversibly comes into equilibrium with its environ-
ment,” can be used in various fields such as industrial ecology or environmental
engineering, in order to use energy more efficiently and minimize harmful
impacts on the environment.
Since the late 1990s, the applications of exergy analysis have been extended
into the realm of resource and environmental analysis, for developing integrated
analytical frameworks. Not only do the merits of this framework make it an
interesting analytical tool for researchers, but also, exergy analysis can be used as
a decision-making tool for policy makers for making sustainable choices.
For example, the impacts of resource depletion are an integral part of envi-
ronmental analysis; yet a major challenge in life cycle impact assessment (LCIA)
is to come up with methods to quantify resource depletion. Due to the fact that
exergy provides a natural basis for assessing the efficiency of resources use, it has
been shown that exergoenvironmental analysis is a more appropriate instrument
to quantify the environmental problem of natural resource depletion. Moreover,
with the aid of exergetic LCA, the immediate estimation of the exergetic effi-
ciency of processes is provided as well as the comparison of different environ-
mental impacts of different options.
This chapter presents a summary of exergoenvironmental analysis, and further,
it will discuss methods to apply exergoenvironmental analysis, namely, cumula-
tive exergy consumption (CExC), exergetic life cycle analysis (ELCA), and
cumulative exergy extraction from the natural environment (CEENE). Finally,
applications in improving resource efficiency and development of sustainable
technologies and processes will be discussed.
Keywords
Exergy analysis · Life cycle-based analysis · Exergoenvironmental · Exergy-
based methods · Exergetic analysis
Exergy Analysis
History
The concept behind exergy is based on “quality of energy.” Sadi Carnot was the first
who showed that the produced work from a certain amount of thermal energy divided
by that amount of thermal energy is less that one, which means that even under ideal
conditions the efficiency of this conversion is less than 100%. Sadi in 1824 showed
that the higher the temperature, the more produced work we have. He names this the
“quality of heat.” This conclusion together with the concept of entropy was introduced
as the second law of thermodynamics by Clausius in 1865 (Frangopoulos 2009).
In subsequent development, Tiat (1868) and Maxwell (1871) added the concept
of “availability” or “available energy” to previous studies. Later, Gibs (1873)
42 Exergy and Life Cycle-Based Analysis 1059
provided an analytical framework to calculate the available energy in a cantina

situation. Stodola’s works in 1898 founded the idea of a relation between entropy
generation and loss of produced work (Frangopoulos 2009).
“Exergy” was assigned to the term “availability” in 1965 by Rant, rooted in the
Greek words “ex” and “ergon,” meaning “from” and “work.” After that, this field of
research advanced dramatically during the years of 1930–1980. The development of
the exergy concept owes a great deal to three main research groups, Keenan et al.
(working on the role of “general available energy”), Obert and Gaggioli (application
of “available energy costing methods” in practical examples), and Tribus and
Y. El-Sayed (developing the concept of “essergy” as a term to measure “departure
from equilibrium”) (Frangopoulos 2009).
Basic Concepts
Today, the exergy of an energy system is defined as the maximum theoretical work
(or shaft work) that can be done by a system when it comes to thermodynamic
equilibrium with the reference system (or the environment); the environment or
reference system is determined by its temperature, pressure, and chemical composi-
tion. Unlike energy which is independent of environment properties, exergy is a
function of both the system and environment properties (Frangopoulos 2009).
The exergy of a system is equal to the sum of physical, kinetic, potential, and
chemical exergies:
Esys ¼ EPH
Sys þ E
KN
þ EPT þ ECH
The physical, kinetic, potential, and chemical exergies are calculated by the
following equations, respectively:
Sys ¼ ðU U 0 Þ þ pðV V 0 Þ T ðS S0 Þ
EPH
mv2
EKN ¼
2
EPH ¼ mgz
X
M
sb ðT, PÞ ¼ gs ðT 0 , P0 Þ
eCH i ð T 0 , P0 Þ g i ð T 0 , P 0 Þ
vi eCH
i¼1
where the subscript 0 represents the properties of the system at the temperature and
pressure of the environment (T0, P0)
U = internal energy
V = Volume
S = Entropy
i = ith chemical element
gi = Gibs function at T0, P0
vi = the stoichiometric coefficient in the reaction

eCH
i = standard chemical exergy
Ibrahim Dincer and Marc A. Rosen (2007, 2012) have described the character-
istics of exergy in a book; some key characteristics of exergy are as follows:
• The situation in which a system is in a complete equilibrium with the reference

system is called the “dead state.” In the dead state, the exergy of the system is
equal to zero.
• The higher the exergy of a system, the more it has deviated from the environ-
mental conditions.
• The exergy and energy of electricity are equal, similar to shaft work.
• An estimation for chemical exergy of fuels for gaseous, liquid, and solid fuels is
0.95–0.98, 0.98–1, and 1–1.04 of the HHV, respectively.
• Despite energy which is a measure of quantity, exergy is a measure of quality.
• Energy cannot be destroyed or produced, while exergy is always destroyed in an
irreversible process. In a reversible process, exergy is not destroyed or produced.
Exergy Efficiencies
In energy system analysis, exergy analysis can be performed by an exergy balance.

Exergy balances can be written as (Dincer and Rosen 2012):
(Exergy in) = (change of exergy contained in the system) + (total exergy output
from the system) + (Exergy destruction due to internal irreversibility)
Ein ¼ ΔEsys þ Eout þ ED
Due to internal irreversibilities such as temperature difference, mixing, expan-

sion, friction, and chemical reactions, exergy can be destroyed. Both exergy balance
and calculation of “entropy generation within the system” can be used to formulate
and calculate exergy destruction. Also, the exergy destruction of a system is equal to
the sum of exergy destruction of all the system components:
ED ¼ T 0 Egen
X
n
ED ¼ ED, k
k¼1
Before addressing exergy efficiency, it is substantial to define exergy loss (ED).

Exergy loss is contributed to the amount of exergy which is not available for useful
work. It is also associated with the transfer of mass or energy to the environment.
Therefore, exergy efficiency can be written as
Exergy output Exergy loss þ Exergy destruction

η¼ ¼1
Exergy input Exergy input
Exergy efficiency is used to find potential exergy recovery in a system and to

discern the components in a system which have lower performances compared to
other components (Frangopoulos 2009).
Also, there is another definition of exergy efficiency, referred to as the “modified
exergetic efficiency.” Given the fact that we can split exergy destruction into
“avoidable exergy efficiency” and “unavoidable exergy efficiency,” the “modified
exergetic efficiency” can be written as
Exergy output
η ¼
Exergy input Unavoidable exergy destruction
Exergy loss þ Avoidable exergy destruction
¼1
Exergy input Unavoidable exergy destruction
Eliminating unavoidable exergy destruction, exergetic efficiency provides

a more realistic performance indicator rather than exergy efficiency. Note
that unavoidable exergy destruction is part of exergy destruction that cannot
be recovered even if the “best available technology (BAT) in the near future” is
applied.
Strengths and Limitations of Exergy Analysis
Energy analysis has a major limitation: not considering the quality of energy. If the
quality of energy is incorporated into the analysis, a different result will be reached.
Thus energy analysis leads to non-optimal choices. With the aid of exergy analysis,
not only is “quantity” considered, but also “quality” of energy flows is taken into
account. Therefore exergy provides a universal method for “rational use of
resources” (Frangopoulos 2009).
Exergy analysis brings insight for understanding the energy conversion process in
a complex energy system and shows “the causes of thermodynamic inefficiencies.”
However, some of these improvements may not be in a match with engineering and
economic limitations. Hence, exergy analysis should be combined with engineering
and economic considerations to find cost-effective and realistic improvement
options.
Ibrahim Dincer and Marc A. Rosen (2007) discussed that as far as suitability is
concerned, the merits of the exergy concept make it a suitable candidate as a
quantifier of the sustainability of a process. They illustrate the potential of exergy
analysis in solving “energy-related sustainable development and environmental
problems” (Dincer and Rosen 2012).
On the other hand, the “lack of a formal procedure in using the results from an
exergy analysis” is weighed as a major limitation of exergy analysis by Tsatsaronis
and Cziesla (2009). They discussed that this weakness could also be considered as a
strength, because it has made exergy analysis a domain of using intuition and
creativity (Frangopoulos 2009).
LCA
Life cycle assessment is a useful method which considers the environmental aspects
of a product, service, or process throughout its life span as a “cradle-to-grave”
approach, from raw material acquisition to production, transportation, use, and
disposal (Scientific Application International Corporation (SAIC) 2006).
ISO 14040 defined LCA as the “compilation and evaluation of the inputs,
outputs and potential environmental impacts of a product system throughout its
life cycle.” The Society of Environmental Toxicology and Chemistry (SETAC) has
presented a detailed description for LCA as the “process to evaluate the environ-
mental burdens associated with a product, process or activity by identifying and
quantifying energy and materials used and wastes released to the environment; to
assess the impact of those energy and material uses and releases to the environ-
ment; and to identify and evaluate opportunities to effect environmental improve-
ments. The assessment includes the entire life cycle of the product, process or
activity, encompassing extracting and processing raw materials; manufacturing;
transportation and distribution; use, re-use, maintenance; recycling; and final
disposal” (Tuker et al. 2004).
As SETAC has stated, this method, to the extent possible, quantifies emissions,
resource depletion, and other environmental and health impacts associated with the
stages that are encompassed in the LCA, and if it is not possible, it depicts a
qualitative picture of the involved environmental burdens in those various stages
(Tuker et al. 2004). Figure 1 illustrates life cycle stages of a product, its inputs,
outputs, and related environmental releases in all phases.
History
Initial development of the concept of life cycle of a product occurred in the nineteen
fifties and sixties in the scope of public purchasing. It was mentioned in a report by
RAND Corporation, by Novick (1959), for the first time as life cycle analysis of cost.
Life cycle analysis was applied first by governments in order to improve budget
management. But it rapidly extended to the private sector to achieve optimization of
system performance and development (Curran 2012).
The first studies which led the life cycle cost analysis to the present concept of life
cycle assessment were done in the realm of waste and energy analysis in late 1960s
and early 1970s, when environmental issues such as resource depletion, pollution
control, and solid waste became important (Guinee et al. 2011).
The period of 1970–1990 was the decades LCA conception (Guinee et al.
2011). However, it was applied with diverging approaches, terminologies, and
results and without a common theoretical framework, due to the lack of interna-
tional scientific discussion and information exchange. In the 1970s to 1980s, LCA was
used by firms to prove market claims. But it was not accepted as an analytical tool,
particularly due to different results obtained from identical case studies (Curran 2012;
Guinee et al. 2011).
Raw Material Extraction Atmospheric Emissions
Materials Waterborne Wastes

Transportation/Manufacturing
Solid Wastes
Use/Reuse/Maintenance
Energy Coproducts
Recycle/Waste Management Other Releases
Fig. 1 Life cycle stages (Adapted from Scientific Application International Corporation (SAIC)
2006)
The abovementioned problem regarding the lack of international scie-

ntific communication about LCA platforms was improved in the 1990s. In
fact, the convergence finally occurred by SETAC’s coordination and ISO’s
standardization in the duration of 1990–2000 which resulted in standardized
frameworks. So the 1990s are known as the standardization decade (Curran
2012; Guinee et al. 2011).
The period of 2000–2010 is known as the decade of elaboration. Increasing
attention to LCA resulted in launching an International Life Cycle Partnership
by the United Nations Environment Programme (UNEP) and the Society of
Environmental Toxicology and Chemistry (SETAC) in 2002, aimed to spread
life cycle thinking, put it into practice, and improve and develop supporting
tools. The continued importance of life cycle thinking has had significant
effects on environmental policy formation, especially in European policy. Life
cycle-based environmental policies have been formed on themes such as acidification,
eutrophication, diffusion of toxic substances, disposal of waste, noise, odor and
air pollution, climate change, and dehydration. It should be mentioned that due to
the increase of LCA demand, divergence in methods has occurred again (Curran 2012;
Guinee et al. 2011).
The next development of life cycle analysis after 2010 is introducing a challeng-
ing new framework, Life Cycle Sustainability Analysis, which broadens the scope of
the current LCA to the three pillars of sustainability: economy, environment, and
society (Curran 2012).
LCA Phases
An LCA comprises of four phases. It starts by goal and scope definition, continues to
inventory analysis, and then proceeds to the impact assessment, and finally it ends
with the interpretation (Curran 2012). Figure 2 illustrated the relationship between
these phases in the life cycle assessment framework, and the following sections will
express more detail about each of them.
Goal and Scope Definition
In this phase the initial plan of the LCA study will be provided by goal and
scope definition. In goal definition, as the first step of a life cycle assessment,
the main context of the assessment should be determined first. Then by determin-
ing the reasons and purposes of carrying out the study, one leads into defining
the desired applications and the related audience of the assessment. Finally, it
should be clarified whether it is necessary to present the results to the public or not
(Scientific Application International Corporation (SAIC) 2006; Curran 2012; Wolf
et al. 2012).
The second step of this phase, scope definition, which depends on the goal
definition, also has several substages. At first, it should determine the product system
to be studied. Then, in order to express and quantify the function of products and
provide a basis for a fair comparison of differences, a functional unit should be
defined. This step should specify which stages are involved in the life cycle of a
product and should be covered in the assessment and is done by defining the system
boundaries, the geographic and time boundaries and the flows, and the environmen-
tal impact categories to be investigated. Scope definition also describes the assump-
tions and impact assessment methods to be applied, the interpretation approach, and
the need for the critical review (Scientific Application International Corporation
(SAIC) 2006; Curran 2012; Wolf et al. 2012).
Fig. 2 Phases of a life cycle

assessment (Scientific Goal & Scope
Application International Definition
Corporation (SAIC) 2006)
Inventory Analysis Interpretation
Impact
Assessment
Inventory Analysis
Life cycle inventory analysis is the second phase, and it should conform to the goal
definition and fulfilling the requirements of the scope defined. According to ISO
14040, in the life cycle inventory (LCI) analysis phase, the collection and quantifi-
cation of the entire product life cycle inputs and outputs is done. The results of this
phase lead to the next step, impacts assessment, which also plays an important role as
feedback to adjust the scope phase assumptions (Curran 2012).
In more detail, LCI includes:
• Identifying the system processes

• Data collection, developing generic LCI data when specific data are not available
and obtaining complementary data for elementary flows (such as resources and
emissions), product flows (goods and services as products), and waste flows (such
as wastewater or solid waste)
• Modeling the life cycle of the system to be analyzed
This phase requires a high amount of data and resources, as quantification is vital
in this stage. In addition, data validation is carried out in this phase as well (Scientific
Application International Corporation (SAIC) 2006; Curran 2012; Joint Research
Centre-Institute for Environment and Sustainability (JRC-IES) 2010).
Impact Assessment
As mentioned before, the LCI results provide the inputs of the subsequent phase, life
cycle impact assessment (LCIA). In fact, LCIA, as the third phase, translates the data
that have been collected and reported in the previous LCI phase into defined impact
categories and corresponding indicators and evaluates the magnitude of potential
human health and environmental impacts in order to address the product-, service-,
or process-related environmental impacts throughout its life cycle from raw material
extraction through production, use, its waste treatment, recycle, and final disposal.
Therefore, the LCIA’s main purpose is to determine the role of the assumed flows in
previous phases in potential environmental problems and their relative importance,
which can provide additional information for LCA practitioners and decision-
makers to interpret the results.
Based on ISO 14042, LCIA consists of mandatory and optional steps which are
illustrated in Fig. 3.
A summary of the LCIA steps is as follows:
• Classification and Characterization: The first mandatory step of LCIA is selection

of impact categories, category indicators, and characterization models in line with
the goal and scope definition phase. It is then followed by the assignment of LCI
Mandatory Elements
Selection of Impact Categories, Category Indicators & Characterization

Models
Assignment of LCI Results (Classification)
Calculation of Category Indicator Results (Characterization)
Category Indicator Results, LCIA Results
Optional Elements
Calculation of the Magnitude of Category Indicator Results Relative to

Reference Information (Normalization)
Grouping
Weigthing
Fig. 3 Mandatory and optional steps of LCIA (Tuker et al. 2004)
results to the selected impact categories (classification). The final step is to

calculate the category indicator result by multiplying the inventory data of LCI
results and characterization factor.
• Normalization and Grouping: In this optional step, the dimensionless, normalized
LCIA results, relative to reference information, will be presented by multiplying
LCIA results with normalization factors. The results will be ranked in accordance
to their importance.
• Weighting and Data Quality Analysis: Weighting enables the possibility of
indicating the difference of various impact categories and aggregating them by
obtaining normalized weighted results using a set of weighting factors. Data
quality analysis deals with reliability of the indicator results (Scientific Applica-
tion International Corporation (SAIC) 2006; Curran 2012; Wolf et al. 2012; Joint
Research Centre-Institute for Environment and Sustainability (JRC-IES) 2010).
Interpretation
The final phase of the LCA starts with identification of significant issues based on
integration and evaluation of both LCI and LCIA results and in relation to the
defined goal and scope definition, considering completeness, sensitivity, and con-
sistency. Interpretation aims to develop conclusions and recommendations,
addresses the limitations of data quality and sensitivity analysis, and also checks
the appropriateness of the first phase assumptions.
Interpretation is useful to help decision-makers to choose the most sustainable
environmentally friendly alternative considering technical, economic, and social
aspects too.
Iterative Approach
LCA is known as an iterative process in its four phases. It starts based on initially
available data of processes, resources, and environmental releases of the case study and
revises the data goal and scope when the uncertainties are too high and does more precise
analysis if the sensitivity analysis points out the requirement of some crucial decisions.
Briefly, this iterative loop approach includes:
• Defining the goal aspects of the study as accurately as possible which leads to an
initial scope definition
• Inventory data collecting
• Process modeling based on the available inventory data
• Calculating life cycle impact assessment (LCIA) results
• First completeness, sensitivity, and consistency check on the initial model
• Revising and improving previous phases (Curran 2012; Wolf et al. 2012)
Figure 4 illustrates these steps.
Strength and Application
Investigating environmental aspects of a product, service, or process life cycle

provides helpful information. Evaluating and interpreting this information presents
a holistic view of environmental impacts, for instance, climate change, toxic effects
on humans and ecosystems, and resource depletion, into one consistent framework
which can determine environmental drawbacks and their improvement potentials
from the raw material extraction stage to the final disposal. Integration of these
impacts over the entire life cycle of the analyzed system helps avoid unwanted
shifting of environmental burdens from one place to another while resolving one
environmental problem (Scientific Application International Corporation (SAIC)
2006; Wolf et al. 2012).
Overall Data Quality

(Accuracy, Precision, Completeness)
Third Iteration
• Better Data for Key
Processes and Flows
Second Iteration
• Revision of Scope Definition
(if necessary)
• Better Data for Key
Processes
First Iteration
• Full Product System
• Specific Data as
Available
• Easily Available
Secondary Data
Time and
Effort
Fig. 4 Iterative structure of LCA (Joint Research Centre-Institute for Environment and Sustain-
ability (JRC-IES) 2010)
This comprehensive approach can be used as a powerful decision-making tool

when comparing different alternatives, considering their major environmental
impacts and their trade-offs. Although LCA cannot determine which option is
sustainable, it can indicate which one is more environmentally friendly. Therefore,
it can play an important role in moving toward sustainable production and consump-
tion through guiding decisions on investment, policy issues, and strategy determi-
nation (Tuker et al. 2004; Curran 2012).
LCA has been used in various fields including modeling bio-based systems, agri-
food industries, supply chain management, end-of-life material management, mining
and minerals processing, forest products, product innovation, food waste and pack-
aging, energy systems, and oil and chemical industries (Curran 2012; Cherubini
et al. 2009; Bhat and Prakash 2009; Nielfa et al. 2015; Matos and Hall 2007;
Rausand and Kawauchi 1999).
Limitations of LCA
Despite the mentioned strengths of LCA, it has several limitations which are
illustrated here. One option is to extend LCA with the help of other methods and
instruments to overcome its constraints.
One limitation is that based on the goal and scope definition, system boundaries
and the considered detail of an LCA may vary to a large extent.
LCA has been known as a data intensive and complex method; therefore,
executing a good LCA is time intensive and costly. Fortunately, analyzing mature
processes and products experience less problems, since these processes have been
optimized before and the required data are available (Curran 2012).
LCA considers only environmental aspects of the entire life cycle of a product,
process, or system, such as emissions and resource depletion. It does not provide any
information about economic and social characteristics, the effects of the product on
humans, for instance, human health, the market mechanism, future effects on
technology development, and rebound effects (Curran 2012; Wolf et al. 2012).
In LCA all processes are assumed to be linear and steady state. In fact, LCA does
not address the time aspect and also localized impacts (Curran 2012). LCA is not
appropriate if the complexity of the system is too high. Generally using this method
requires high expertise.
Finally, even though LCA can provide useful information for decision-makers
and strategy planners, it cannot change the decision-making process itself. In
addition, it does not address the risks, costs, and benefits (Curran 2012).
Exergy-Based Methods
Decreasing the thermodynamic inefficiencies and environmental impacts of a system

requires defining their sources and the way these are formed. Even though energy is
useful for modeling processes, it has some weaknesses when applied as an analysis
tool, especially in identifying process inefficiencies (Dewulf et al. 2008).
Thermodynamic inefficiencies of a system are caused by irreversibilities within
the system, exergy destruction, and exergy transfer to the environment (exergy loss).
Therefore, exergy-based analysis, which is based on the second law of thermody-
namics, is implemented to overcome the mentioned problems in energy analysis. Far
beyond technical analysis, it is applied to reveal the sources and magnitude of the
inefficiencies in order to reduce them. Moreover, since exergy analysis is applicable
throughout the entire production and consumption chain, from resource to environ-
mental releases, it can be used in the environmental impact assessment as well
(Dewulf et al. 2008; Morosuk et al. 2016).
Exergetic Analysis
Cumulative Exergy Consumption/Demand

Production processes which consist of various steps from raw material extraction
to final products need to consume energy. Therefore, cumulative energy consump-
tion (CEnC) has become an important tool to investigate the energy consumption
in the production chain. This analysis which is also called industrial energy
analysis or energy costing is applied to determine the required increase in fuel
extraction based on planned changes in production of products and evaluate the
influence of fuel price changes in product costs. However, this analysis tool does
have several drawbacks; it does not take into account the consumption of
non-energetic raw materials, the differentiation of the quality of various kinds of
energy, and the degree of the thermodynamic imperfection. Some of these limita-
tions can be improved by applying the second law of thermodynamics and the
concept of exergy which is able to evaluate the energy quality and the degree of
thermodynamic imperfection of the energy transformation (Szargut and Morris
1987; Szargut 1987).
Applying the second law of thermodynamics has resulted into an exergy
analysis called cumulative exergy consumption (CExC) methods which consider
all stages of a process from natural resources to final products (Dewulf et al. 2008).
The main idea of these methods is to consider any production processes as a set of
elemental processes, each causing input exergy increase, exergy destruction in
their internal irreversibilities, and adding exergy value to the final product. There-
fore, the final product has a cumulative exergy content that can be calculated when
the production process is known (Dewulf et al. 2008; Sciubba and Wall 2007).
CExC methods include the cumulative exergy demand (CExD), the cumulative
exergy extraction from the natural environment (CEENE), the industrial cumula-
tive exergy consumption (ICEC), and the ecological cumulative exergy consump-
tion (ECEC) method. The main difference between the first three methods and the
last one is the system boundary. CExD, CEENE, and ICEC consider the techno-
sphere technosphere (also called anthrosphere is the part of the ecosphere that is
modified by man for use in human activities) as their system boundary, to assess
the exergy content of natural resources extracted by the technosphere from the
ecosphere, while the ECEC method’s system boundary is the ecosystem (ecosys-
tem comprises the atmosphere, biosphere, hydrosphere, and lithosphere). It is also
applied for goods and services processes which are considered in the ecosphere
boundary (Huysman et al. 2015).
CExC methods have the potential to be extended to the life cycle of the product
and determine the potential improvements in each stage and also enable the com-
parison of different alternatives. They are used as comprehensive resource-based life
cycle impact assessment (LCIA) methods to qualify and quantify all kinds of
resources extracted into a single score which does not need weighting factors and
avoids the double counting problem (Dewulf et al. 2016). Calculation methods of the
CExC index will be illustrated in the following:
• The sequence method: In this method the CExC index is calculated by the
analysis of the production process network. The network should be divided into
levels and the analysis should be started from the final process. Therefore, the first
level provides the final step of the production set processes, and the last level
contains the production of engines and installation required for level 1. The
exergy consumption related to the intermediate product consumption in subse-
quent levels should be taken into account too. Finally, the exergy consumption
values should be summed up over all the levels (Szargut and Morris 1987).
• Balances of CExC method: Setting a series of balance equations of cumulative
consumption in a production process can give an exact calculation of the CExC
index. These equations calculate the sum of the cumulative consumptions in the
production chain related to the delivered intermediate products and natural
resources extracted immediately from the environment. In fact, in this method
the CExC index is subject to the conservation law. The following equation
expresses the balance of CExC of the kth natural resource for production of the
unit of the major product of the jth process in the final step of production:
X X
r kj þ r ki fij ¼ r ki aij þ Bkj
i i
where
rkj = partial CExC index of the kth natural resource per unit of the jth product
fij, aij = coefficients of the by-production and of consumption of the ith intermediate
product per unit of the jth product, in the final step of production
Bkj = immediate exergy consumption of the kth natural resource per unit of the jth
product in the final step of the production of this product (Szargut and Morris 1987)
Therefore, CExC methods are applied as an analytical tool to:
• Calculate the required changes in fuel and raw material measures based on the
planned variation in the production process.
• Evaluate the influence of fuel and raw material price change on the final product
costs.
• Compare different methods based on comparing cumulative consumption of raw
materials.
• Evaluate the possibility of raw material and fuel consumption changes as a result
of applying new production method.
• Analyze the cumulative effects of using waste products.
• Analyze the cumulative effects of raw material and fuel substitution due to their
possible scarcity (Szargut and Morris 1987).
Exergoeconomic Analysis
According to monetary cost approaches and neoclassical economics, the monetary

cost of a commodity is a function of several factors: material, energy, labor, capital,
and environmental cost. Considering the last three factors, which are called the
“externalities,” researchers have proposed various methods for their “internaliza-
tion.” Assessing the monetary value of material, energy, and labor can be easily
done, but the problem will occur in monetary accounting of environmental impacts,
which could possibly be solved by thermodynamics (Valero 1998; Rocco et al. 2014;
Serra and Cuadra 2009; Sciubba 2013). Therefore, exergoeconomic analysis, which
exploits both economic and thermodynamic concepts to overcome the mentioned
problems, was developed. In the following, two exergoeconomic methods will be
discussed.
Thermoeconomics
Thermoeconomics (TE) is a powerful analytical tool with a physico-mathematical
background which is used for energy-economic-ecological analyses and optimiza-
tion (Valero 1998; Valero et al. 1994). Thermoeconomics is a monetary cost tech-
nique, presented as a science which connects the second law of thermodynamics
with economics. This method is founded on exergy costing principle that assumes
exergy as the rational costing basis since exergy defines the real value of commod-
ities based on physical criteria, local optimization, and operation diagnosis (Valero
1998; Rocco et al. 2014; Serra and Cuadra 2009). Thermoeconomics applies the
usual procedures of engineering accounting, relating each component’s price to their
operating parameters and exergetic efficiency, in order to price the specific exergy
content of the stream, by using monetary balances on components of the system
(Dewulf et al. 2008; Sciubba and Wall 2007). In fact, this method allocates cost of
material and energy flows based on their exergy contents to become homogenous
with other factors, capital and labor, as all of them are expressed in monetary terms
(Sciubba 2013). This process is done on the basis of an estimation of each sub-
process loss, measured by its exergy destruction, and calculation of the influence of
upstream irreversibilities on downstream exergetic efficiencies (Dewulf et al. 2008).
Improving the exergetic efficiency of a system generally results in increasing capital
costs and decreasing operating costs; therefore, in this situation, thermoeconomics
can determine the best trade-off between total system cost and its efficiency, aimed at
obtaining the minimum economic cost (Rocco et al. 2014).
Thermoeconomics has two main groups of methods:
• Cost accounting methods: these methods use average costs for price assessment.
• Optimization methods: these methods apply marginal costs to minimize the total
costs (Serra and Cuadra 2009).
Thermoeconomics has proven useful to process engineers and energy conversion

managers, due to its superiority compared to energy analysis in cost allocating and
determining losses in complex systems. This technique is also applied in the analysis
and optimization of industrial plants such as CHP plants, chemical distillation,
refinery processes, water desalination, and tri-generation plants (Dewulf et al. 2008).
In spite of these applications, thermoeconomics suffers from several drawbacks:
• Dependence of its results on market considerations

• Having difficulty to formulate scarce resources, since their specific exergy is
assumed to be near zero (when the stream is directly extracted from the
environment)
• Lack of correct physical and thermodynamical links of effluent exergy and its
toxicity in environmental impacts remediation activities cost accounting
• Nonlinearity of product cost function in complex systems (Rocco et al. 2014)
Extended Exergy Accounting

Extended exergy accounting (EEA) is an exergoeconomic method that measures
the primary exergy embodied in products coming from consumed resources during
their life cycle production chain, including the externalities (Sciubba et al. 2008;
Sciubba 2011). As illustrated before, the monetary production cost of a commodity
consists of material, energy, capital, labor, and environmental remediation costs;
the last three factors, the externalities, are the reason for the term “extended,” since
previous methods neglected these additional terms in their analysis. Moreover,
“accounting” refers to the processes’ unavoidable irreversibilities and destructions
(Sciubba 2001).
EEA calculation starts by defining a reference state, evaluating the mass and
energy balances of all subprocesses, and calculating the physical and chemical
conditions of all input and output streams. Moreover, it is necessary to define the
waste treatment processes in order to acquire the essential information. So the
equation can be presented as follows:
EEA ¼ CEC þ EC þ EL þ EO
CEC represents the cumulative exergy consumption due to the process inputs; EC,
EL, and EO refer to the exergy equivalent of monetary flows, working labor, and
pollution removal costs, respectively (Sciubba 2011; Chen et al. 2014). They are
formulated as

J
EL ¼ α Ein
yr

J
EC ¼ β EL
yr
in which Ein is the influx of exergy to the process and α and β are the econometric
constants that depend on the system structure, time, and space (Sciubba 2011; Chen
et al. 2014).
The equivalent cost of environmental effluent treatment and retuning them to the
reference condition is calculated by the capital exergy equivalent, eeC, and the
required investment in environmental remediation, Iinv:
EO ¼ eeC I inv
Ein
eeC ¼ α β
M2
where M2 is the monetary circulation (Sciubba 2011; Chen et al. 2014).
These equations show that EEA is a time- and space-dependent method which
represents more information of the economic, social, and environmental patterns of a
society (Sciubba 2011).
In comparison of EEA to other methods, EEA uses exergy content of all flows to
measure their energy content, as in classical exergy analysis. It considers the whole
life cycle of a production process as well as the LCA. In addition, measuring the
embodied exergy of all inputs and outputs of the studied system is similar to the
cumulative exergy content. EEA and TE can both convert all inhomogeneous
quantities, such as material and labor, into homogeneous terms. But it should be
mentioned that unlike EEA, the original TE did not consider the environmental
remediation cost at first (Rocco et al. 2014; Sciubba et al. 2008).
EEA as an analysis tool which can compute the resource consumption in the
life cycle of a product, considering social, economic, and environmental aspects
in homogeneous terms, can provide broader information than previous methods
to decision-makers. However, it has some drawbacks such as the need for
standardization and formalization and improvements of the required databases
and the need for more investigation to define exergy equivalent of labor and
capital (Rocco et al. 2014).
Exergoenvironmental Analysis
Society’s increased awareness of environmental issues necessitates ecological

performance improvement of processes and systems from both thermodynamic
and environmental viewpoints (Curran 2012; Morosuk et al. 2016). These eval-
uations and improvements require a deep understanding of the relation of exergy
and environment. This relation clears the real thermodynamic inefficiencies and
their formation sources, the environmental impacts related to them, and the
potential to improve efficiencies and reduce the environmental impacts (Morosuk
et al. 2016).
The relation of exergy and the environment can be divided into three main
categories:
• Waste emission: Waste emissions are considered to have exergy value since they
are not in equilibrium with the surrounding environment and have the potential to
cause change. The impact of emissions can be quantified in two ways:
(a) calculating the exergy loss in the natural environment and society caused by
health effects and assigning them to living organisms, loss of natural environ-
ment, and human life years and (b) calculating the required exergy to abate the
emissions.
• Resources: Natural resources have exergy value due to not being in the equi-
librium with the environment. Therefore, resource consumption in production
and consumption processes will result in environmental damage. Different
exergy-based methods to resource accounting include (a) material flow analy-
sis, (b) statistical entropy function, (c) using exergy analysis in order to achieve
better resource management, and (d), the most applied one, cumulative exergy
consumption.
• Order destruction: As the exergy of an ordered system is more than a chaotic one,
the destruction of order or chaos creation is considered as an environmental
damage (Curran 2012; Dewulf et al. 2008).
As mentioned before, an LCA considers the entire life cycle of a product and
evaluates and quantifies the environmental impacts in each stage, from material
extraction to the waste disposal and emission releases. Nevertheless, LCA lacks the
thermodynamic assessment which can be compensated by extending LCA with
exergy considerations. In fact, exergy can be used for environmental purposes as
well as industrial and economic ones (Curran 2012).
Exergetic life cycle assessment or exergoenvironmental analysis (ELCA), using
the same framework and objectives as LCA, but with a different approach, is defined
as the exergy analysis of a full life cycle (Fig. 5). It is carried out at the component
level of a system which addresses the thermodynamic irreversibilities during the life
cycle of the system and points out each component’s contribution to the environ-
mental impacts of the system and the possibilities to reduce those environmental
impacts (Curran 2012; Morosuk et al. 2016; Hirs 2002).
This method can help decision-makers improve the society’s sustainability, since
this analysis tool considers both cost- and life cycle-related environmental impacts.
Figure 6 illustrates the relation between exergy efficiency, environmental impacts,
and sustainability. Increasing exergy efficiency leads to reducing environmental
impacts and as a result approaching higher sustainability (Curran 2012).
Materials Raw Material Extraction Products
Energy Coproducts
Exergy Emissions
Exergy
Transportation/Manufacturing
Use/Reuse/Maintenance
Recycle/Waste Management
Fig. 5 Exergoenvironmental framework (Curran 2012)

Environmental Sustainability
Impacts
0 100
Exergy Efficiency
Fig. 6 Relation of exergy efficiency, environmental impacts, and sustainability (Curran 2012)
1. Goal and scope definition

2. Modeling of the intended system
3. Exergy analysis
Investigation of
4. Life cycle assessment improved option
5. Assignment of environmental impacts to exergy streams
6. Calculation of exergoenvironmental variables
7. Exergoenvironmental evaluation
8. Determination of improved option
Minimized environmental
impacts of the system
Fig. 7 Exergoenvironmental method structure (Meyer et al. 2009)
Exergoenvironmental analysis consists of three steps which are also presented in

Fig. 7:
• A detailed exergy analysis

• A life cycle assessment of the environmental impacts
• Assigning the environmental impacts to the exergy streams and calculating the
exergoenvironmental variables and at last an exergoenvironmental evaluation
(Curran 2012; Morosuk et al. 2016; Meyer et al. 2009)
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Magnetic and Nanostructural
Properties of Cobalt–Zinc Ferrite 43
for Environmental Sensors
A.-H. El Foulani, R. C. Pullar, M. Amjoud, K. Ouzaouit, and

A. Aamouche
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1080
Experimental Set-Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1082
Sample Preparation Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1082
Characterization Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1083
Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084
Thermal Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084
Crystallographic Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084
Specific Surface Area and Porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1087
Morphology and Microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1087
Magnetic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1089
Catalytic Testing and Ethanol Conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1090
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1093
A.-H. El Foulani
MSISM Research Team, Department of Physics, Polydisciplinary Faculty of Safi,
Cadi Ayyad University, Safi, Morocco
R. C. Pullar
Department of Materials and Ceramic Engineering, Department of Physics, CICECO – Aveiro
Institute of Materials, University of Aveiro, Aveiro, Portugal
M. Amjoud
Laboratory of Condensed Matter and Nanostructures, Faculty of Science and Technology,
Cadi Ayyad University, Marrakech, Morocco
K. Ouzaouit
REMINEX research center, Groupe Managem, Marrakech/Medina, Morocco
A. Aamouche (*)
Applied Sciences National School (ENSA), Cadi Ayyad University, Marrakech, Morocco
e-mail: a.aamouche@uca.ma

https://doi.org/10.1007/978-3-319-73645-7_85
1080 A.-H. El Foulani et al.
Abstract
In this study, we compare nanoparticles (NPs) of Co0.5Zn0.5Fe2O4 spinel ferrite
produced by a novel simple synthetic technique with those made by standard
co-precipitation, sol-gel, and hydrothermal methods. The novel process is based
on the addition of a very small amount of ethanol (only 2 vol% in water with a
low ethanol:metals molar ratio of 0.5:1, not a co-solvent) during co-precipitation
to synthesize a nanopowder, which formed single-phase magnetic spinel ferrite
when heated at 700 C. This technique produced cobalt–zinc ferrite NPs smaller
than those formed by the other methods, with an average crystallite size of 17 nm
calculated from X-Ray Diffraction and NPs sizes around 30 nm observed by
scanning electron microscopy. A surface area of 32 m2/g, and a total pore volume
of about 0.56 cm3/g, were determined by the BET isotherm. The best catalytic
capabilities for converting ethanol vapor to CO, CO2, and H2O, as well as
magnetic properties, were obtained for Co0.5Zn0.5Fe2O4 synthesized by the
ethanol-assisted co-precipitation. The ethanol conversion rate rapidly increased
above 175 C, and the total conversion of ethanol was achieved at a relatively low
temperature of 230 C. This sample also had the largest magnetization of 58.2 A
m2 kg1 at 3 T, and a very small, near superparamagnetic, coercivity.
Keywords
Semiconductor sensors · Ferrite nanoparticles · Catalytic proprieties · Magnetic
proprieties · Ethanol oxidation · Scanning electron Microscopy · Vibrating
sample Magnetometer · Thermo gravimetric analysis · Ethanol-assisted
co-precipitation
Introduction
Many current concerns regarding environmental protection are focused on air quality
for industry, cities, and households. Important changes and improvements need to
be made to address environmental issues. Environmental pollution is due in a large
part to enormous industrial growth, especially in developing countries. Strong
international market demands for volatile organic compounds (VOCs) is a serious
environmental problem because some of them have toxic or carcinogenic properties
(Tsai 2016). They can also react with nitrogen oxides and oxygen from the air
to form harmful ozone: VOC + NOx + O2 + hν ! O3+ + other products (Jirátováa
et al. 2016). To reduce the emission of VOCs in the air, industrialists have applied the
total oxidation of VOCs to carbon dioxide and water. In the literature, researchers
have a similar interest in using the catalytic process instead of thermal combustion in
the oxidation of VOCs. At the industrial level, catalysts containing noble metals are
currently used because they have shown high activity and stability, but their cost
limits the use of this type of catalyst (Spivey 1987; Rymeša et al. 2002). In this study,
a new, cheaper catalyst based on a transition metal oxide (cobalt–zinc ferrite) was
developed.
43 Magnetic and Nanostructural Properties of Cobalt–Zinc Ferrite for. . . 1081
Ferrite compounds can be used as catalysts as they are highly selective and stable,
particularly for the N-type semiconductors (Woo et al. 2016). Ferrites are iron-oxide
based materials, usually containing other transition, and they have been extensively
studied for their high density (Gadkari et al. 2010), catalytic (Zhihao and Lide 1998),
magnetic, and electrical applications (Dube and Darshane 1993; Wolf et al. 2001).
Spinel ferrites of the formula MFe2O4, with a cubic structure, have been reported
as materials sensitive to both oxidizing and reducing gas (Lalauze et al. 1992;
Sberveglieri 1995; Chen et al. 2000); a wide variety of transition metal cations
(M = Co, Zn, Ni, etc.) may be easily incorporated into the structure. When made as
nanoparticles, they have a powerful surface activity, due to their small particle size
and enormous surface area (Liu et al. 1995; Suo et al. 1997). By taking into account
the fact that the catalysis phenomena take place essentially on the surface of the
material (Zafeiratos et al. 2012), the surface morphology also has an essential role in
the catalytic efficiency (Liu and Norskov 2001).
Cobalt ferrite (CoFe2O4) is a well-known hard magnetic material with a large
magnetization of around 80 A m2 kg1 when in bulk form, but with lower magne-
tization and very low coercivity when formed as nanoparticles, tending towards
being superparamagnetic as they approach 20 nm in diameter with a reduced
magnetization of ~50 A m2 kg1 (Rajendran et al. 2001). These properties are highly
dependent on the size, shape, and phase purity of these nanoparticles (NPs), so it is
necessary to develop simple processes to control CoFe2O4 nanoparticle stoichiom-
etry and texture. Pure ZnFe2O4 is poorly magnetic with a magnetization of 10 A m2
kg1 or less, but the magnetic properties of the mixed cobalt–zinc spinel ferrites
have been studied (Chithraa et al. 2017), and with an initial substitution of Zn for Co
the magnetization increases, giving a maximum at room temperature with 25%
substitution of Co by Zn. 46 nm diameter nanoparticles of Co0.5Zn0.5Fe2O4 made
by sol-gel and heated to 900 C/2 h had a magnetization of ~55 A m2 kg1, with
near-zero coercivity (Chithraa et al. 2017).
Many routes are adopted for cobalt–zinc ferrite NPs production. Chemical syn-
thesis of nanoscale particles was studied by transition metal ion reduction (Klabunde
et al. 1994), by aqueous colloidal solutions separations (Cabuil et al. 1995), in the
presence of an external magnetic field (Blums 1996), in bicontinuous and lamellar
solutions (Pileni et al. 1996), by template-assisted sol-gel (He 2012a), or mechani-
cally alloyed by high-energy ball milling (Ismail et al. 2014; Zulkimi et al. 2014).
Solid solutions of nonstoichiometric mixed cobalt–zinc ferrite nanoparticles were
optimized using atomic absorption spectroscopy, energy-dispersive X-ray spectros-
copy, and transmission electron microscopy techniques (Coppola et al. 2016).
For the same purpose, other authors had used X-ray diffraction and Raman scatter-
ing (Phan et al. 2017). In our previous article, we monitored the catalytic behav-
ior using infrared spectroscopy of Co0.5Zn0.5Fe2O4 ferrite NPs synthesized using
co-precipitation method (El Foulani et al. 2017). A number of synthesis techniques
have been studied to determine the most reliable method to produce catalytic
and magnetic spinels such as, decomposition (Ali Zamanian and Behnamghader
2016), chemical precipitation (Rajendran et al. 2001; Hedayati et al. 2016;
Economos 2006), sol-gel (Lou et al. 2007; Singhal et al. 2001), self-combustion
(Iftimie et al. 2005), citrate routes (Gopal Reddy et al. 2000), and co-precipitation
(Hankare et al. 2009; Tao et al. 2000). The co-precipitation way is the simplest and
effective for oxide multicomponent preparation (Tao et al. 2000).
In this chapter, we compare the magnetic properties and the catalytic efficiency
towards ethanol of ferrite nanoparticles Co0.5Zn0.5Fe2O4 made by four differ-
ent methods standard co-precipitation, an ethanol-assisted co-precipitation,
hydrothermal synthesis, and sol-gel synthesis. This innovative ethanol-assisted
co-precipitation is not like the ethanol–water co-solvent techniques reported in the
past, as it only involves a very small amount of ethanol (2 vol% ethanol in water)
with a low ethanol:metals molar ratio of 0.5:1, in similar quantities to compounds
used as surfactants in nanosynthesis.
Experimental Set-Up
Sample Preparation Methods
Co0.5Zn0.5Fe2O4 nanoparticles were prepared by four different methods. All the

chemical reagents FeCl24H2O, Co(NO3)26H2O and ZnCl22H2O were supplied
by Sigma-Aldrich, of analytical grade, and used without further purification.
For co-precipitation, the precursors were mixed in the stoichiometric ratio of
Co:Zn:Fe = 0.5:0.5:2 in 80 ml deionized water, with a weight ratio of metals:
water = 3.3:100, and stirred until a clear solution was obtained. The NaOH precip-
itating agent (1 mol/l) was added dropwise to the solution, until a pH of 11 was
obtained. The resulting suspension was heated to 70 C with constant stirring at
800 rpm for 1 h. The resulting brown precipitate was washed thoroughly with
deionized water, and then dried in air in an oven at 100 C. The milled powder
was calcined in air at 700 C for 8 h.
The second method was ethanol-assisted co-precipitation, similar to the method
above except for the addition to the salt solution of a small amount of ethanol, before
precipitation. The ethanol was added to the salt solution before precipitation at a
molar ratio of ethanol:metals of 0.5:1, and the volume ratio ethanol/water was 0.02,
i.e., only 2 vol% ethanol, so it was not in sufficient quantities to be considered a
co-solvent.
The third method investigated was hydrothermal synthesis, using the same
reagents and precipitating agent and the same molar ratios as for the standard
co-precipitation above. The mixture was dissolved in 60 ml of deionized water,
put in a Teflon autoclave with a total volume 100 ml, and the autoclave was placed in
an oven at 120 C/48 h. The brown precipitates were washed, dried, milled, and
calcined in air in a furnace at 700 C/8 h.
The fourth technique studied was sol-gel synthesis, again with the same precursor
metal salts in the same ratios. These three salts were separately dissolved in the
minimum amount of deionized water required, and after heating at 80–90 C, all
three solutions were mixed together at room temperature. Citric acid (99% purity,
Sigma-Aldrich) was added to the resulting solution with the molar ratio of metals:
citric acid = 1:1, followed by ethylene glycol (99.5% purity, Sigma-Aldrich) with
the molar ratio metals:EG = 1:1, to form a colloidal solution. The solution was
stirred and heated at 80 C until gel formation. After heating at 120 C/12 h in the
oven, the gel became dry in places, and after a section ignited (usually on the edge), a
combustion wave spread spontaneously throughout the gel, converting it to a loose
black powder containing very fine crystals. Any residual organics were removed,
and the calcination is completed by heating the powder in air in a furnace at
700 C/3 h. In all four cases, the heating and cooling rates for the calcination step
was 10 C per minute.
Characterization Methods
Thermo gravimetric analysis (TGA) were carried out on the precipitates dried in air
at 100 C using a SETARAM Labsys Evo – gas option TG-DTA up to 1000 C at a
heating rate of 10 C/min in air. Determination of phase purity and identification
of the samples were performed by X-ray diffraction (XRD) using a Bruker diffrac-
tometer, D8 ADVANCED model. The XRD patterns were taken between 10–80
with a step size 0.02 using Cu ka radiation (λ = 1.5406 Å) at room temperature.
The operating parameters were a beam current of 20 mA and integration times of
20 s with an acceleration voltage of 30 kV. The crystallite sizes were calculated with
the Debye-Scherrer formula using the corrected full width at half maximum (βhkl)
value of the most intense (311) peak (JCPDS file numbers: 22-1086 and 22-1012).
The Lattice parameters were calculated and refined using the least-squares method
with the X’Pert Plus and Unitcell programs. The specific surface area of calcined
powders was determined using a Quantachrome Autosorb iQ instrument with the use
of nitrogen as an analytical gas. The operating conditions were bath temperature of
77.35 K, degassing temperature of 350 C/21 h. Scanning electron microscopy
(SEM) was carried out on a Hitachi S-4100 at 25 kV on samples coated with carbon.
The magnetic properties were measured using a vibrating sample magnetometer
(VSM, Cryogenics) at 300 K and magnetic fields up to 3 T. The sample temperature
was stabilized at 300 K, and the maximum field ramp rate was 0.25 T/min.
The device sensitivity is rated up to 10.6 A m2 kg1, and the maximum recorded
temperature drift was 0.05 K, with typical values of 0.01 K.
Catalytic Measurements
A catalytic test was performed at atmospheric pressure in a micropilot reactor tubular
glass with continuous flow (Fig. 1). The mass of catalyst introduced was 200 mg.
Ethanol was put in a classic saturator maintained at 20 C and atmospheric pressure.
Ethanol vapor was conveyed by air as a carrier gas with a flow rate of 20 ml/min,
through a stainless steel pipe heated to 80 C to a U-shaped reactor, which is itself
contained in a tubular furnace to regulate the temperature. The catalytic tests were
carried out over a temperature range of 100–350 C, which was measured using a
thermocouple projecting into the center of the chamber. The gas at the outlet of the
(GC)
Air
Gas
chromatography
Ethanol Reactor
Fig. 1 Experimental setup of the catalytic measurements coupled with a gas chromatography unit
reactor was analyzed by gas chromatography (GC) with an Agilent 7890A chro-
matograph, and data processing was carried out using the Cerity program.
Thermal Analysis
Typical curves TGA of the dried sample synthesized by the ethanol-assisted

co-precipitation method are presented in Fig. 2. The initial mass of the sample
was 31 mg. The initial weight loss of 1.08% between 40 and 100 C was attributed to
loss of physically absorbed water or ethanol due to further drying-out of the material.
The greater loss of 2.56% between 100 C and 400 C was attributed to a combi-
nation of the loss of chemically absorbed water and OH species on the particle
surface, any remaining nitrate groups from the Co(NO3)2 precursor, and the loss of
any nonstoichiometric oxygen species during the calcination step and the formation
of the ferrite phase, which typically occurs above 250–300 C. The small, further
loss of 0.50% between 400 C and 900 C could be due to the removal of any
remaining persistent chloride ions, which have been seen to remain up to
800–1000 C in ferrites made from precipitated halide salts (Pullar et al. 2001).
Based on the results obtained by the thermal analysis, the optimum calcination
temperature was chosen to be 700 C for 8 h.
Crystallographic Analysis
The XRD patterns of the four powders after calcination at 700 C are shown in Fig. 3.
All the peaks are well matched with a cubic phase spinel ferrite, as confirmed from
JCPDS file numbers: 22-1086 and 22-1012. The position of the peaks and relative
0.05
0
dTGA
0.0
–0.5
–0.05
–1
–0.1
–1.5
dTGA (mg/min)
–0.15
TGA (%)
–2
–0.25
–2.5
–0.2
–3
–0.3
–3.5 TGA
–4 –0.35
–4.5 –0.4
–0.45
100 200 300 400 500 600 700 800 900
Temperature (°C)
Fig. 2 TGA curves of ferrite Co0.5Zn0.5Fe2O4 synthesized by the ethanol-assisted co-precipitation

method
Fig. 3 XRD patterns of Co0.5Zn0.5Fe2O4 powders, after calcination at 700 C, produced by four
different synthetic routes: (a) co-precipitation (b) ethanol-assisted co-precipitation with, (c) hydro-
thermal, and d) sol-gel
intensities of the XRD patterns confirm that the samples all formed single-phase spinel
Co0.5Zn0.5Fe2O4 ferrite, indexed in a cubic symmetry spinel structure, and with no
evidence of any secondary crystalline phases.
The crystallite size was obtained using the Debye-Scherrer method (Lalauze et al.
1992), in which the average size of the crystallites can be estimated by applying the
following equation:
kλ
D¼
βhkl cos θ
where D = crystallite size, k = shape factor (~0.9), λ = X-Ray wavelength

(1.5406 Å), θ = Bragg angle of the most intense (100%) XRD peak, and
βhkl = corrected full width at half maximum of the peak. It should be noticed that
this technique is only an approximation, becomes less reliable for smaller crystallite
sizes below 100 nm, and reflects the average crystallite size, which cannot be
equated to particle (or nanoparticle) size in the absence of other evidence, such as
SEM or low coercivity proving them to be single nanocrystals. Nevertheless, it is a
useful tool for comparing the degree of crystallinity and the likely trend in particle
size between these four powders.
The dependence of the catalytic/magnetic properties of ferrites on small particle size
is well established, and generally the catalytic efficiency increases simultaneously with
the reduction in crystallite size, while it is more complicated for magnetic properties,
which typically reach a maximum as size decreases, and then decrease with further
decreases in size as the critical magnetic domain size is approached (Ali Zamanian and
Behnamghader 2016; Hedayati et al. 2016; Economos 2006; Lou et al. 2007; Singhal
et al. 2001; Iftimie et al. 2005; Gopal Reddy et al. 2000; Hankare et al. 2009; Tao et al.
2000). Reducing the crystallite size can also accompany an increase in the strength and
hardness of a material (Tsai 2016). The calculated crystallite sizes are shown in Table 1.
The largest size was found for the standard co-precipitation route at 105 nm, with the
other three routes all producing much smaller sizes. The hydrothermal and sol-gel
routes were broadly similar at 42 and 30 nm, respectively, while the ethanol-assisted
co-precipitation route resulted in a significantly smaller size of only 17 nm.
This suggests that the ethanol has a great effect during the co-precipitation process.
We suggest that the added ethanol could limit nucleation, by breaking the agglomer-
ation of the initial NPs formed, since it can replace the water molecules around the
nucleus and by decreasing the critical aggregation parameter (Li et al. 2005), resulting
in a finer nanomaterial, and essentially behaving similarly to a surfactant. For this this
reason, such a small amount of ethanol has such a significant effect.
Refinement of lattice parameters by the least squares method showed that all the
peaks are indexed in the face-centered cubic spinel system. The crystallographic
results obtained for the cobalt–zinc ferrite calcined at 700 C for the four different
synthesis routes shows that there is little difference between them, although gener-
ally the products of the two co-precipitation routes showed slightly smaller values
than those from the sol-gel and hydrothermal routes, the latter giving the largest
values. The values of crystalline parameters are listed in Table 1. The addition of
ethanol has significantly decreased the a parameter and volume of the cell, which are
given by the literature as 8.407 Å and 594.187 Å3, respectively, for Co0.5Zn0.5Fe2O4
(Nikam et al. 2015).
Table 1 Average crystallite size and lattice parameters for Co0.5Zn0.5Fe2O4 powders, calcined at
700 C, according to the synthesis routes used
Diffraction
angle of Average a Lattice
(311) peak βhkl crystallite parameter Unit cell volume
Synthetic route ( ) (Rad) size (nm) (Å) (Å3)
Co-precipitation 36.888 0.001395 105 8.39 0.02 592.0800 4.3839
Ethanol-assisted 37.066 0.008582 17 8.37 0.01 587.5393 3.6482
co-precipitation
Hydrothermal 36.614 0.003436 42 8.44 0.01 603.2331 4.1161
Sol-gel 36.991 0.004814 30 8.41 0.00 594.9159 0.4400
Specific Surface Area and Porosity
The grain size, porosity, and specific surface area (SSA) greatly control the catalytic
activity of a material, because the interaction between the gas and the catalyst occurs
on the surface (Punnoose et al. 2007). Hence, the use of nanomaterials with a large
surface/volume ratio can significantly improve gas adsorption phenomena. Gas
molecules are adsorbed more easily on porous materials (Zhu et al. 2008), as the
surface is essentially made of micropores and mesopores.
Table 2 shows the evolution of the specific surface area, the average pore size and
total pore volume, depending on the synthetic route. As with the XRD crystallite
sizes, the standard co-precipitation and hydrothermal methods gave the samples
with lower surface areas and pore volumes, while the ethanol-assisted
co-precipitation and sol-gel processes lead to the formation of more porous
Co0.5Zn0.5Fe2O4 powder with higher surface area. It is worth noting that the etha-
nol-assisted co-precipitation produced the largest SSA at 32.36 m2/g (which
corresponds to the smallest particle/grain size) and highest pore volume
(~0.56 cm3/g). This is considerably larger than other reported values for
Co0.5Zn0.5Fe2O4 ferrites, of between 5 and 19.5 m2/g (Yasenevz et al. 2011; Wang
et al. 2012). Therefore, the addition of a small amount (2 vol%) of ethanol to the
water improves the specific surface area, along with the creation of a larger number
of open/accessible pores in the material (~0.56 cm3/g vs. ~0.34 cm3/g without
ethanol). It should be noted that the nanopores were of a similar size, ~4–5 nm,
for all the four synthesis routes. It should also be noted that, as with the XRD data,
the sol-gel route gave the second largest SSA and pore volume, in this case
approaching the values of the ethanol-assisted co-precipitation.
Morphology and Microstructure
SEM images show that the morphology of samples prepared through the four
different techniques varies depending on the preparation process (Fig. 4). In general,
Table 2 The specific surface area, average pore size, and total pore volume prepared by the
synthetic routes
Specific surface area Average pore The total pore volume
Synthetic route (m2/g) size (nm) (cm3/g)
Co-precipitation 21.79 4.589 0.33847
Ethanol-assisted 32.36 5.495 0.56421
co-precipitation
Hydrothermal 23.08 4.276 0.33400
Sol-gel 30.65 5.226 0.54215
Fig. 4 SEM images of Co0.5Zn0.5Fe2O4 powders, after calcination at 700 C, prepared with
different synthesis methods: (a) standard co-precipitation, (b) ethanol-assisted co-precipitation,
(c) hydrothermal, and (d) sol-gel
the morphology of the particles is a mixture of nanospheres and plates, with a wide
distribution of the grain size in the range of 30–250 nm. Nevertheless, it can be
observed that the smallest grain size is found in the samples made by ethanol-
assisted co-precipitation (Fig. 4b), with most particles being well-defined and very
small at around 30–50 nm, and some larger, more platy grains between 100 nm and
120 nm (see inset image, Fig. 4b). The smallest grains in the powder made from the
sol-gel process are similarly sized, but this also contains larger, even more platy
grains, as large as 250 nm in diameter (Fig. 4d). The standard co-precipitation and
hydrothermal processes have resulted in fewer of the smallest particles, and an
increased number of the larger grains, explaining their lower surface areas. However,
the larger grains appear to be thicker, and less platy, than those seen in the sol-gel
sample. In the absence of any TEM evidence, the SEM images suggest that the very
smallest grains could be single nanocrystals or bicrystals, as they are approaching the
average XRD crystallite sizes, but the majority of the grains will probably be
polycrystalline nanoparticles. The variation in particle size and coalescence behavior
of the agglomerated particles could be due to differing interfacial surface tension
phenomena during the different synthesis conditions.
Magnetic Properties
Co0.5Zn0.5Fe2O4 ferrite should be a strongly ferromagnetic material, with a reported

bulk magnetization of around 80 A m2 kg1 (He 2012b), and a coercivity that can
vary greatly depending if the grains are oriented or not. Co0.5Zn0.5Fe2O4 ferrite
nanoparticles have been studied as potential thermomagnetic materials for medical
treatments via magnetic hyperthermia, and they become superparamagnetic at
room temperature below around 10 nm (Arulmurugan et al. 2005), smaller than
the 20 nm critical size reported for pure CoFe2O4 NPs (Rajendran et al. 2001).
Coercivity (Hc) approaches zero as their size decreases below this, and Hc as low as
0.7 kA m1 (8.8 Oe) has been reported for 8.4 nm Co0.5Zn0.5Fe2O4 nanoparticles
(Arulmurugan et al. 2005). Their saturation magnetization (Ms) also decreases with
size, and values of Ms = 39.6 A m2 kg1 were reported for these 8.4 nm NPs
(Jaffrezic-Renault et al. 2002), compared to 55 A m2 kg1 for 46 nm NPs (Chithraa
et al. 2017). The room temperature magnetization loops of our Co0.5Zn0.5Fe2O4
ferrites, heated to 700 C, made by the four routes, are shown in Fig. 5.
60
Co0.5Zn0.5Fe2O4
40
20
M (A m2 kg–1)
–20 1 Co-precipitation
1 2 Ethanol assisted Co-precipitation
–40 4 3 Hydrothermal
4 Sol-gel
3
–60 2
–3 –2 –1 0 1 2 3
Fig. 5 Magnetization loops of Co0.5Zn0.5Fe2O4 powders, after calcination at 700 C, made with
different synthesis methods: (1) co-precipitation, (2) ethanol-assisted co-precipitation, (3) hydro-
thermal, and (4) sol-gel
As expected, they are all very soft ferrites, with low Hc values. Apart from the sol-gel
route, they all appear to be virtually superparamagnetic, with very little coercivity at
zero field. The sol-gel sample has a slightly wider hysteresis loop, with a definite Hc of
around 32 kA m1 (400 Oe), requiring an applied field of 0.04 T to reduce the
magnetization to zero and then reverse it. This may be because it contains the more
plate-like particles, which may be oriented with respect to the applied magnetic field,
inducing and increased coercivity, despite the small average particle size. The largest
magnetization was found for the ethanol-assisted co-precipitation, which although it
resulted in the smallest particles, also gave a material with a reasonably high magne-
tization of 58.2 A m2 kg1 at 3 T. The magnetization of the hydrothermal sample was
second highest, having an Ms (at 3 T) of 53.2 A m2 kg1, and with values of 37.7 A m2
kg1 and 32.3 A m2 kg1 for the sol-gel and co-precipitated samples, respectively.
Therefore, the changes in magnetization do not follow the changes in particle size/
crystallite size/SSA, and other features such as particle morphology, and variation in
oxidation state (e.g., presence of Fe2+ ions) play a role. Nevertheless, the sample made
by our ethanol-assisted co-precipitation route has the superior magnetic properties as
a strongly magnetic yet very soft/superparamagnetic ferrite, as well as having the
smallest size. The very low, almost superparamagnetic coercivity values for this
show that it the NPs are nearing the critical size at which this becomes super-
paramagnetic reported as being 20 nm for CoFe2O4 (Rajendran et al. 2001) and
<45 nm for Co0.5Zn0.5Fe2O4 (Chithraa et al. 2017).
Catalytic Testing and Ethanol Conversion
The chemical composition of our material, Co0.5Zn0.5Fe2O4, is modified in the

presence of an oxidizing or reducing gas (Arulmurugan et al. 2005). In the presence
of ethanol vapor (a reducing gas), many reactions are possible on the surface layer,
particularly as a function of temperature. For example, the following reactions have
been identified (Cheong and Lee 2006):
In the presence of oxygen (an oxidizing gas):
½ O2 ðgasÞ þ 1e ! O ðadsorbedÞ
In the presence of ethanol (a reducing gas):
CH3 CH2 OH ðgasÞ þ O ðadsorbedÞ !CH3 CHO ðadsorbedÞ þ H2 O þ e !

T 230 C
CH3 CHO ðadsorbedÞ þ 4 O ðadsorbedÞ !CO þ CO2 þ 2H2O þ 4e !

T > 230 C
Other reactive oxygen species such as O2 are also possible at such temperatures.
Figure 6 illustrates the results of the ethanol catalysis measurements with
Co0.5Zn0.5Fe2O4 synthesized by the four different methods. The best result was
Ethanol conversion rate

100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
0 50 100 150 200 250 300 350 400
Temperature en °C
1 2 3 4
Fig. 6 Ethanol conversion rates for Co0.5Zn0.5Fe2O4 powders, after calcination at 700 C, synthe-
sized with different methods: (1) co-precipitation, (2) ethanol-assisted co-precipitation, (3) hydro-
thermal, and (4) sol-gel
obtained for the material synthesized by the ethanol-assisted co-precipitation

method, in which the conversion rate rapidly increased above 175 C, and the
total conversion of ethanol was achieved at a relatively low temperature of
230 C. This temperature is rather moderate, when compared with those of the
literature (Poulopoulos 2016; Legendre and Cornet 1972; Yao 1984). The ethanol
conversion of the other powders followed in the sequence of synthesis by sol-gel,
hydrothermal, and standard co-precipitation routes, with the total conversion
of ethanol occurring at 260 C, 310 C, and 340 C, respectively. Therefore, the
catalytic activity of Co0.5Zn0.5Fe2O4 spinel ferrite is related to the crystallite size and
specific surface area, which determine the efficiency of these materials towards
ethanol vapor in the presence of oxygen ions on their surfaces. Many studies have
shown that the surface properties of the catalyst are important in studying catalysis
because of the vital relationship between the catalytic activity and the catalyst surface
(Wei et al. 2011).
Conclusions
Environmental pollution is due in a large part to enormous industrial growth.

This creates the need for serious environmental monitoring, but the high cost
currently limits the control and monitoring of air quality in many countries and
situations. The use of devices based on semiconductor sensors, namely from the
ferrite, would be cheaper and easier than the current analytical techniques, and the
detection operates via the interaction of the gas and a sensitive material, modifying
physico-chemical properties (electrical conductivity, optical properties, etc.)
resulting from the chemical reaction between the gas molecules and the oxygen
adsorbed on the metal oxide surface. The present chapter was an opportunity to
review a wide range of semiconductor-based sensing materials and how to increase
the sensitivity of these sensors with the addition of catalytic metals and non-metals.
The novel process employed here involves the addition of small amount of
ethanol (2:1 ratio of metals:ethanol, 2 vol% in water) to the water during the
co-precipitation to synthesize a precursor nanopowder, which formed single-phase
magnetic Co0.5Zn0.5Fe2O4 spinel ferrite when heated at 700 C. The quantity of
ethanol used is similar to the amounts of compounds used as surfactants in nano-
synthesis. This simple technique produced cobalt–zinc ferrite nanoparticles smaller
than those formed by standard co-precipitation, sol-gel, and hydrothermal
methods, with an average crystallite size of 17 nm calculated from XRD, particle
sizes as small as 30 nm observed by SEM, a large surface area of 32 m2/g and a high
pore volume of 0.56 cm3/g evaluated from BET isotherm. We suggest that the added
ethanol limits nucleation, reprecipitation, and growth on the particles surfaces during
precipitation, resulting in a finer nanomaterial. These microstructural improvements
promote a larger exchange surface with the gas for many applications like catalysis
and gas sensing. The catalytic properties were tested with ethanol as a reducing gas
(converting to CO, CO2, and H2O by reaction on the ferrite surface) using
Co0.5Zn0.5Fe2O4 catalyst powders prepared through four methods. The best result
was obtained for Co0.5Zn0.5Fe2O4 synthesized by the ethanol-assisted
co-precipitation method, in which the conversion rate rapidly increased above
175 C, and the total conversion of ethanol was achieved at a relatively low
temperature of 230 C. This sample also had the largest magnetization of
58.2 A m2kg1 at 3 T, and a very small coercivity, giving an almost super-
paramagnetic hysteresis loop, suggesting it consisted of NPs near the critical super-
paramagnetic domain diameters of 20–45 nm. Therefore, this study has
demonstrated the beneficial effect of a small amount of ethanol added to the water
for preparing cobalt–zinc ferrite nanoparticles through the ethanol-assisted
co-precipitation method, on the physicochemical features, magnetic and catalytic
properties of ferrite Co0.5Zn0.5Fe2O4 powder. We also expect this material will be
applicable as a gas sensor candidate for monitoring air pollution.
Cross-References
▶ Air Pollution
▶ Management of Residues from Air Pollution Control Systems
Study of Delhi City
World
▶ Monitoring and Risk Analysis of PAHs in the Environment
▶ New Trends in Environmental Analysis

▶ Remediation of Industrial and Automobile Exhausts for Environmental
Management
Acknowledgments This work was supported by the Portugal-Morocco bilateral collaboration

grant FCT/CNRST-2015/2016 Proc. № 441.00. This work was partly carried out at CICECO-
Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM /50011/2013)
financed by national funds through the FCT/MEC.
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New Trends in Environmental Analysis
44
Awad Ageel Al-rashdi
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1098
Recent Developments in Environmentally Preferable Sample Preparation Techniques . . . . . . 1099
Immunoaffinity Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1100
Molecular Imprinted Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1101
Ionic Liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1102
Deep Eutectic Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1102
Surface Active Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1103
Supercritical Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1104
Bio-Derived Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1105
New Adsorbent Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1105
Polymer-Based Monoliths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1105
Restricted-Access Material Sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1106
Nanomaterials as Sorbent Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1107
Metallic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1108
Mixed Metal Oxide Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1108
Carbon Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1109
Silicon-Based Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1110
Polymeric Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1111
Magnetic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1112
Application of Nanomaterials as Sorbents for Environmental Analysis . . . . . . . . . . . . . . . . . . . . . . 1114
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1115
A. A. Al-rashdi (*)
Department of Chemistry, Center for Scientific Research (QCSR), Al-Qunfudah University
College, Umm Al-Qura University, Makkah Al-Mukarramah, Al-Qunfudah, Saudi Arabia
e-mail: aarashdi@uqu.edu.sa

https://doi.org/10.1007/978-3-319-73645-7_86
1098 A. A. Al-rashdi
Abstract
Rapid advances in technology, chromatographic separation methods, and analyt-
ical methods are required for the early recognition and accurate estimation of
environmental contaminants. A recent trend has been to extract and analyze the
maximum number of chemical compounds simultaneously, which has led to the
development of simple, rapid, accurate, and environmentally friendly analytical
methods. The main goal of these methods is to save time, expense, and labor.
Furthermore, many substances are harmful even at very low concentrations, but
they may be difficult to analyze directly. Thus, highly effective extraction
methods are necessary. This chapter provides a brief summary of recent trends
in analytical chemistry, which stem from the basic principles of green chemistry.
Various nanoparticles and their uses in environmental analysis are also discussed.
Furthermore, the basic principles of immunoaffinity chromatography are exam-
ined because of its importance in biological analysis. Finally, this chapter
explores the environmentally friendly methods using ionic liquids, deep eutectic
solvents, surface active agents, supercritical water, and bioderived solvents in
chemical analysis.
Keywords
Environmental friendliness · Sample preparation · Restricted materials ·
Imprinted polymers · Nanomaterials · Selectivity · Sensitivity · Monolithic ·
Silica · Separation · Mechanical toughness · Immunoaffinity chromatography ·
Porous · Sorbent · Microextraction · Metallic nanoparticles · Metal oxide ·
Magnetic nanoparticles · Carbon nanomaterials · Fluorine C60 · Carbon
nanotubes · Graphite · Silicon · Polymeric nanoparticles · Nanofibers ·
Nanofilms · Ionic liquids · Deep eutectic · Supercritical water · Bio-derived
Introduction
Environmental analysis involves several steps: sampling, field sample handling,

sample preparation, quantification, and statistical evaluation. Each one of these
steps is important for obtaining accurate results. However, these analytical steps
are successive, so the next step cannot start until the previous one has been finished.
The overall performance of the analytical procedure is affected greatly by each step
of the analytical process. Sample preparation is a critical component of the analytical
process. Sample preparation may include filtration, physical parameter adjustments,
extraction, clean-up, and pre-concentration.
Increasing public concern has focused on the protection of the environment.
Thus, chemists, including analytical chemists, are striving to make their activities
more environmentally friendly. However, the analytical methods used to assess the
levels of pollutants may in fact be a source of significant pollution. Large amounts of
pollutants may be generated during the sample preparation step in particular. To
44 New Trends in Environmental Analysis 1099
address this concern, researchers have been developing sample preparation tech-
niques that use small amounts of organic solvents, or none at all.
Trace analysis of the contaminants in environmental samples is a challenging task
due to the complexity of sample matrices, the limited number of certified reference
materials, the major difficulties associated with the long-term monitoring of a large
number of pollutants, and the diversity of interfering compounds. To investigate the
progress and trends in environmental analysis, we examined a large number of
published papers. Through this concentrated survey, we found that developments
in environmental analysis can be divided into three distinct periods of times:
pre-1970s, 1970 to 2000, and 2000 to the present time. Before the 1970s, analytical
chemists focused on the development of selective extraction techniques, replacing
the traditionally used liquid-liquid extraction with high-resolution gas
chromatography-mass spectrometry. This allowed environmental scientists to inves-
tigate small quantities of pollutants (e.g., chlorinated pesticides, petroleum hydro-
carbons, poly aromatic hydrocarbons) in the environment quantitatively and
quantitatively. From 1970 to 2000, environmental analytical chemists developed
sample preparation techniques for ever smaller quantities of new and emerging
pollutants. Great improvements were achieved during this period of time in terms
of sensitivity and selectivity. Certainly, this has been the trend in the past 20 years,
since liquid chromatography-mass spectrometry started being used in the environ-
mental field. This technique has allowed the estimation of large numbers of pollut-
ants simultaneously, even at very low levels.
Currently, the latest trend in environmental analysis is to expand analytical
strategies in order to monitor as many pollutants as possible, as well as to investigate
their effects on flora, fauna, and public health. The simultaneous extraction of the
maximum possible number of compounds allows for simple, rapid, and generic
sample treatments. As a result, environmental analysis is now characterized by
environmental friendliness, low cost, miniaturization, automation, and simplicity.
The next section discusses new trends in the analysis of some emerging pollutants.
Recent Developments in Environmentally Preferable Sample

Preparation Techniques
In the identification of analytes in environmental samples, the extraction of target

analytes from within the sample is the main consideration. The accurate determina-
tion of target analytes from complex sample matrices requires very efficient and
selective extraction methods. Furthermore, sample preparation and extraction are
often the most time-consuming steps in the analytical process. Thus, researchers
have been investigating new analytical methods that are highly efficient and envi-
ronmentally friendly, based on the principles of green chemistry.
Investigators have been focusing on the development of more efficient extraction
and clean-up approaches. Some recent trends in this area include the following:
• Automation through the coupling of sample preparation units and detection

systems
• Application of nanostructured sorbents
• Application of eco-friendly approaches
Sample preparation techniques can be classified into two types: those targeted to
solid samples and those targeted to liquid samples. For solid samples, sample
preparation and extraction generally use conventional methods, such as liquid-
solid extraction. To improve performance, this technique can be combined with
microwave-assisted extraction or ultrasound assisted extraction, solvent-reduced
techniques such as matrix solid-phase dispersion and liquid-phase micro extraction,
and more sophisticated methods such as supercritical fluid extraction and pressurized
liquid extraction, which have been intensively reviewed elsewhere.
In liquid samples, extraction is mainly carried out using online or offline
approaches to solid phase extraction. Increasing attention has been focused on
improvements to the adsorbent materials, including restricted access materials
(RAMs), molecularly imprinted polymers (MIPs), adsorbents based on nano-
materials and immunosorbents, techniques based on large-size particles, and online
turbulent flow chromatography. In addition, different solvent-reduced techniques,
such as solid-phase micro extraction (SPME) and stir-bar sorptive extraction, are
also suitable for liquid samples. The following sections describe recent develop-
ments and trends in sample preparation and extraction, as well as the wide variety of
materials and extraction techniques that are suitable for environmental applications.
Immunoaffinity Chromatography
Immunoaffinity chromatography (IAC) is a special type of affinity chromatography

that uses antibodies and its derivatives in a stationary phase. The principle of this
technique is based on the highly specific affinity between an antigen and its antibody.
High selectivity and attractive binding of antibodies for the given analytes has drawn
great attention to immobilized ligands for affinity chromatography (Fitzgerald et al.
2011). In IAC, antibody ligands are supported on the surface of a solid matrix, such
as carbohydrate-related media, synthetic organic supports, or magnetic beads, to
form a stationary phase; the target analyte acts as the mobile phase.
IAC was first developed in the 1950s as a purification technique, especially for
food and biological analysis. Since then, the applications of IAC have expanded to
include immunodepletion, direct sample analysis, chromatographic immunoassays,
and combined analysis methods. The selective binding of antibodies is crucial. This
binding is a result of four different types of reversible non-covalent interactions:
ionic interactions, hydrogen bonds, van der Waals bonds, and hydrophobic interac-
tions. The extent of this binding is based on the strength and the kinetics of this
interaction, which in turn are related to the amount of immobilized antibody, the
concentration of the applied target, and the flow rate used for binding. The four main
types of antibodies used in IAC are polyclonal antibodies, auto-antibodies,
monoclonal antibodies, and anti-idiotypic antibodies, which are produced inside the
cell lines within the body. Recently, antibodies with high binding affinities have been
produced artificially.
The key factors that greatly affect the performance of IAC are the biological
affinity pair, the matrix support, the immobilization coupling chemistry, and the
effective elution conditions. The advantages of IAC include high selectivity, good
reproducibility, and the high degrees of purity that can be obtained for polar analytes
in a complex matrix. Some limitations of this technique include low stability against
solvents, leakage of ligands, a higher flow rate that reduces the binding efficiency,
low productivity, high pH, and high temperature. Some applications of IAC were
investigated by Froschl et al. (1997).
Molecular Imprinted Polymers
MIPs are cross-linked polymers that contain highly selective recognition sites
around a template molecule, bound covalently or non-covalently to functional
monomers. MIPs have been widely used in capillary electrochromatography, enan-
tiomeric separations, biomimetic molecular recognition sensors, heterogeneous
catalysis in organic synthesis, and immunoassays. Applications of MIPs in sample
preparation techniques have been described by Ferrera et al. (2004). The specific
recognition property of MIPs is based on the molecular memory imprinted in the
polymer, which is capable of selectively binding the target. In analytical separation,
MIPs act as a stationary phase that can recognize the template as a target.
MIPs can be synthesized using three different imprinting approaches: covalent,
non-covalent, and semi-covalent. Paleologos et al. (2005) discussed the different
strategies used for the synthesis of MIPs. Non-covalent procedures are probably the
most widely used due to the flexibility of the selection of the possible template
molecules and the suitable functional monomers (Bagheri and Saraji 2003).
Generally, MIPs are synthesized by copolymerization of cross-linking monomers.
A high concentration of polymers around the template result in a highly cross-linked
network polymer. Once the polymerization has taken place, the templates are
removed, thus providing binding sites with shapes, sizes, and functionalities that
are complementary to the target analyte. With these tailor-made binding sites, MIPs
recognize the given template physically (shape and size) and chemically (functional
groups of the molecules). The resulting imprinted polymers have long-term stability,
high specificity, recognition ability, good physical robustness, and low cost, as well
as resistance to a wide range of temperatures, pH levels, and pressures. Among the
main advantages of these materials are the ease of synthesis and reversible adsorp-
tion/release of the target analyte. The advantages of MIPs allow for extensive
applications in analytical chemistry, where they are used for the separation and
detection of many compounds in food, biology, and environmental fields. However,
some drawbacks of MIPs must be considered, including slow mass transfer, irregular
shapes with low reproducibility, incomplete template removal, and poor selectivity
(Namera et al. 2011).
Ionic Liquid
Ionic liquids are ion compounds that can be prepared from organic cations and
organic or inorganic anions. They often exist in a liquid phase at temperatures below
100 C. These solvents have unique properties such as incombustibility, good
solubility, negligible vapor pressure, high heat resistance, good conductivity, high
synthetic flexibility, reusability, and tunable viscosity. Although ionic liquids are in a
liquid phase, they are not simple liquids; furthermore, their ions are generally
asymmetric. The bonding forces of ionic liquids are more complex than those
found in conventional salts. The relatively large size of one or both ions and their
asymmetry are the reasons for the low melting points of these substances.
In analytical chemistry, ionic liquids are considered to be green solvents for most of
the chemical processes and are used as a good alternative to conventional solvents Ho
et al. (2014). Some of these properties, such as thermal stability, depend on the anionic
part; others, such as viscosity, depend on the cationic. Taking this into account, the
properties can be adjusted for the purposes of specific chemical applications by
changing the cationic or ionic properties. For this reason, ionic liquids are referred
to as “designer solvents” and can be used in many different extraction techniques. In
SPE and SPME techniques, ionic liquids can be used as safe alternatives to traditional
solvents, with high extraction efficiency and low extraction time. In SPE, ionic liquids
were used in the stationary phase by covalently linking them with silica or organic
polymers, In the SPME technique, ionic liquids have been used extensively as a fiber
material coating due to their high viscosity and high selectivity. The bonding of ionic
liquids to the silica surface provides higher stability, preventing loss during the
extraction or elution steps as well as the possibility of reusing the SPE device after
the soft cleaning process. However, some problems have been noted for the use of
ionic liquids in analytical applications: relatively high cost, difficulty in obtaining
them at very high purity levels, hygroscopic nature, and toxicity (Hijo et al. 2016).
Deep Eutectic Solvents
Deep eutectic solvents (DESs) are a new type of green solvents that have recently
attracted a lot of attention in many fields of science and technology. DESs have
characteristics similar to that of ionic liquids, but they have some additional advan-
tages. Therefore, DESs are sometimes considered to be a subclass of ionic liquids.
They are less expensive, easier to prepare, less toxic, and are often biodegradable,
which makes them an important alternative to traditional solvents in many analytical
chemistry applications. Unfortunately, their high viscosity and their solid state at
room temperature could be harmful.
Recently, natural deep eutectic solvents (NADESs) were introduced as suitable
alternatives to traditional solvents in extraction methods. NADESs have all the
advantages of DESs in addition to being more environmentally friendly due to
their natural origins. DESs and NADESs typically have a network of hydrogen
bond acceptors (HBAs) and hydrogen bond donors (HBDs); therefore, they are
preferred for the decomposition processes of target analytes. Quaternary ammonium

salts are often used as HBAs in DESs, whereas the HBDs may be alcohols, polyols,
carbohydrates, amines, carboxylic acids, or amides.
DESs may be used for several applications in analytical chemistry, including the
following:
1. Microextraction of the target elements from complex samples followed by detec-

tion using variety of analytical instruments
2. The development of nanoparticles, silica, and sorbents, among others, to improve
their extraction performance
3. Decomposition or digestion of solid samples
4. Chromatographic separation as a mobile-phase additive/modifier
Microextraction methods based on DESs may be considered as a new type of

homogeneous liquid-liquid extraction (HLLE). Generally, in DES-based HLLE
methods, a homogeneous solution is produced after the addition of a water-miscible
DES solution. Thus, the addition of an emulsifier solvent (usually tetrahydrofuran) is
necessary to gain a turbid solution. Sonication in an ultrasonic bath is often used to
isolate aggregated DES droplets into an aqueous solution. The separation of the two
phases is usually achieved by centrifugation. Based on the complex used to config-
ure DESs, they can be divided into the following three groups (Karimi et al. 2016):
Type I Y/MClx; M = Zn; Sn; Fe; Al; Ga

Type II Y/MClx.yH2O; M = Cr; Co; Cu; Ni; Fe; Ca; Mg; La
Type III Y/HBDs(RZ) with Z = –CONH2–COOH; –OH
The basic physicochemical properties of DESs makes them suitable for use as
green solvents in analytical chemistry, including their freezing points, density,
viscosity, polarization, ionic conductivity, acidity, and alkalinity. DESs have the
lowest freezing points of all compounds. Most DESs are denser than water, with a
higher viscosity at room temperature and less ionic conductivity. The presence of
hydrogen bonds makes them polar in nature.
In summary, DESs and NADESs have a number of unique features: good
biocompatibility, safe, biodegradable, environmentally friendly, easy preparation
procedures, not active with water, low cost, available compounds, ionic nature,
relatively high polarity, many design options, and a large number of cations or anions
(Yousefi et al. 2017). However, they do have some limitations, including high
viscosity, slow mass transfer (and thus lack of extraction efficiency), and difficulties
in filtration, decantation, and dissolution of the target analytes (Tang et al. 2014).
Surface Active Agents
Surface active agents (SAAs) are amphiphilic molecules in which the head is a polar
group and the tail is a hydrophilic group. They can be classified as follows:
(1) anionic substances containing anionic groups at the head, (2) cationic substances
containing cationic groups at the head, (3) zwitterionic substances containing dual
cationic and ionic groups at the similar molecule, and (4) non-ionic substances.
These materials are also called surfactants.
Usually, SAAs occur in very diluted aqueous solutions. After increasing the
specific concentration to the critical micelle concentration, surfactant molecules
begin to assemble to form clusters; micelles and a cloudy solution are then created.
The shape of micelles depends on the specific conditions of the solution and the type
of SAA molecule (Paleologos et al. 2005). The micelles are considered to be a
colloid system, in which the particles are smaller than the wavelength of visible light;
thus, the solution is transparent. In aqueous and other polar solutions, surfactant
molecules accumulate by directing their polar tails toward the center. Thus,
non-polar regions form within the polar solution. If the center is non-polar, reversed
micelles are created, with their heads inside the structure. The mechanism of
absorption of the compounds in the micellar phase is called solubilization.
Analytically, the main characteristic of these molecules is their high capacity to
solubilize various compounds. Thus, the solubility of many compounds that are poorly
soluble in water can be improved significantly when a micellar phase is dispersed in an
aqueous solution. After extraction, the surfactant-rich layer can be separated from the
solution by centrifugation or by adjusting appropriate conditions, such as temperature
and pressure. This technique is characterized by its ease, low cost, nontoxicity, sim-
plicity, and high capacity to concentrate a broad range of analytes.
The extraction process of target compounds using surfactants includes first
dissolving the compounds for the micelle particles. That is, the mean compounds
in their original matrix are bonded to the micelles, clouding the solution by adjusting
the temperature and pressure. The next step is separation of the rich phase of micelles
that contain the target analyte (Ferrera et al. 2004). This technique can be used in the
field of analytical chemistry for the extraction of persistent organic pollutants, such
as heavy metals, polyaromatic hydrocarbons, and pesticides, from environmental
samples. In recent years, this technique has been used in the bioanalysis of antibi-
otics and food analysis.
Supercritical Water
Water is generally the best and most widely used solvent. Water has very unique
features including a hydrogen-bonded structure, high boiling point, high polarity, and
acidic and alkaline properties. Heating water to a temperature in between 100 C and
370 C—that is, higher than the boiling point and below the critical point—and
increasing the pressure above the value of the atmospheric pressure to maintain a liquid
state leads to changes in the physiochemical properties of water. At this degree of
heating and under these conditions, the permittivity, surface tension, and viscosity of
water increases, while the polarity and diffusion rate decreases. This water is called
supercritical water. The dielectric constant of water is an important factor in this
process, because it decreases at high temperatures from 80 to 27, which is near the
dielectric constant of ethanol at room temperature (Froschl et al. 1997). This property
means that a large number of polar and non-polar compounds are soluble in water.
Extraction using superheated water as a solvent has a number of advantages.
Supercritical water is considered to be a good alternative to traditional solvents in
extraction methods because it is nontoxic, easy to prepare, readily available, and
inexpensive. It is a selective, fast, and environmentally friendly method to extract a
wide range of analytes from polar to non-polar compounds. However, the extraction
efficiency of water is limited. Furthermore, extracting analytes from aqueous solu-
tions is sometimes accompanied by some problems. In most supercritical water
extraction methods, oxygen is removed using a stream of nitrogen; sometimes, the
pH is adjusted to increase selectivity for a specific analyte. In addition, small
amounts of organic solvents may be added to the supercritical water solution to
improve the separation efficiency. In most cases, supercritical water extraction yields
a comparable amount to that obtained using similar extraction techniques, such as
Soxhlet extraction or super fluid extraction (Shabkhiz et al. 2016).
Bio-Derived Solvents
Bio-derived solvents are produced from biomass in a biorefinery. After use, they can
decompose naturally. Biomass includes a wide range of materials such as forest
products, aquatic biomass (e.g., microalgae), energy crops, and waste materials.
These materials have many properties such as low toxicity, environmental suitability,
and natural degradability. For these reasons and because renewable feedstocks are
used for production (which is one of the principles of green chemistry), these
materials are classified as the most important green solvents in chemistry (Li et al.
2016). However, not all bio-derived solvents are used as green solvents in extraction
because they do not meet the basic requirements for green chemistry, including low
toxicity, non-ignitability, good selectivity, high capacity toward the analyte, high
interfacial tension, reasonable cost, and low viscosity. Among the bio-derived
solvents, biodiesels and terpenes are considered to be the most suitable for solvent
extraction (Smith et al. 2016).
New Adsorbent Materials
The discovery of a number of new adsorbent materials has greatly improved the
extraction, clean-up, and pre-concentration methods for target analytes of environ-
mental samples in terms of selectivity and sensitivity.
Polymer-Based Monoliths
Polymer-based monolithic materials were first introduced in 1989. The use of silica-
based monolithic particles has greatly contributed to the development of separation
methods for different pollutants in environmental samples. These materials have a

number of potential advantages, including low cost, mechanical toughness, high
stability, long service life, low environmental impact, thermal resistance, high
specific surface area, easy scale-up, and the flexibility to adjust pore shape and
size by varying the composition of precursors for the separation of different target
analytes (e.g., small-size pharmaceutical molecules, peptidic analytes, large molec-
ular weight compounds). Moreover, the morphology and pore structure of the
resulting monoliths can be changed based on the composition of precursors (e.g.,
silica source), the solvent, and the polymer. In addition, the use of monolithic
particles results in fast separation and short analysis time.
Monolithic particles can be provided in the stationary phase inside the chromato-
graphic column. Monolithic columns are durable, pressure stable, and allow for
separation at a wide range of flow rates. Moreover, the excellent mass transfer
properties of these materials allows for acceptable capacity, even at high flow
rates, thus resulting in high separation efficiency with good average recovery of
many analytes. By adjusting the pore structure of the stationary phase, the pressure
drop can be improved as a function of the column performance.
Monolithic columns are characterized by the existence of a large number of
theoretical plates (more than 1 million), which greatly improves the chromatographic
separation process. The first monolithic polymer used for solid phase extraction was
poly(styrene-co-divinylbenzene). Stationary phase-based monoliths are available in
more than 10 different sorbent materials, such as C2, C8, and C18; they can be
modified easily with a variety of materials. These materials are also available in many
formats that can be easily automated. Other favorable features are decreased fouling
and plugging, and thus increased lifetime and ease of cleaning of particulates
aggregated on the channel walls. The major disadvantages of monolithic sorbents
include potential low radial heat transfer rate (and thus difficulty in temperature
control for thin-walled monoliths), heat transfer from the monolith to the interior
reactor wall, complexity, and high costs for extruding and installation on an industrial
scale. Other drawbacks of monoliths are their lower surface areas in comparison with
conventional solid-phase materials and less commercially available chemistries.
Restricted-Access Material Sorbents
Restricted-access sorbents are porous chromatographic materials that are designed

for the direct and repetitive injection of complex biological matrices without an
extensive sample preparation procedure. Therefore, they are of interest for improv-
ing analytical parameters and decreasing total analysis time. RAMs generally exhibit
an interior phase for selectivity retarding small molecules and an external layer for
avoiding proteins. They have several different structures, but their mechanism of
separation is identical: the low-molecular-weight compounds are selectively retained
by hydrophobic, hydrophilic, ionic, or affinity interactions through a physical or
chemical diffusion hydrophilic barrier; at the same time, the macromolecules are
excluded by physical or chemical means, or a combination of the two.
RAMs sorbents have been used extensively in solid phase extraction (SPE), solid
phase microextraction, and stir-bar sorptive extraction techniques. However, most of
the analytical methodologies using RAM sorbents are employed in SPE methods.
Some selected applications of RAM sorbents in sample preparation were investi-
gated by (Wang et al. 2010).
The barrier that prevents the entry of high-molecular-weight compounds into the
hydrophobic part of the stationary phase occurs through different mechanisms.
Generally, the small pores of the outer stationary phase (with a typical size of
60 A ) act as a physical barrier that is accessible only to low-molecular-weight
molecules. The presence of hydrophilic functional groups on the surface of a sorbent
provides a chemical barrier, which avoids the irreversible interaction of
macromolecules.
RAMs are ideal for automation, purification, and sample pre-treatment. They are
developed to retain analytes and exclude macromolecules from within untreated
biological samples. RAMs are used widely as purification methods in chromato-
graphic separation for biological samples. Two approaches have already been used:
direct mode/single column and column switching.
The advantages of RAM sorbent materials include their long life and low cost. In
addition, they are an organic solvent that is typically not very time consuming.
Because sample pre-treatment is not needed, the analysis is very rapid, simple, and
environmentally safe. Some applications of RAM sorbents in analytical sample
preparation were explored by Shen et al. (2011).
Nanomaterials as Sorbent Materials
Nanomaterials have been increasingly explored as sorbents for environmental anal-

ysis. The term “nanomaterial” has been used to describe a sub-micron material that
can be created with at least one dimension that is less than 100 nm. Nanoparticles are
of great interest because of their chemical and physical properties. The flexibility of
synthesized and modified nanoparticles makes them suitable for different analytical
applications, which may be useful in other fields as well. In analytical chemistry,
nanoparticles are of interest for the extraction and pre-concentration of different
targets within samples. When different materials (e.g., carbon, gold, silver, etc.) are
scaled from micro to nano size, their physical and chemical properties change. One
of the most interesting properties of nanomaterials is their high service area. Nano-
materials can thus be used as sorbents for sample preparation, with high adsorption
capacity, high enrichment factor, easy functionalization, and reusability.
The nanoparticles used in different extraction techniques can be classified as
metallic, mixed metal oxide, magnetic, carbonaceous, silicon, nanofibers, nanowires,
or polymeric nanomaterials. Nanosorbents are very different from most traditional
sorbents because they are formed from nanoparticles with exceptional physiochemical
properties. The characteristics of these materials include high surface-to-volume ratios,
high thermal stability, and the formation of non-covalent bonds with organic com-
pounds, which has resulted in rapid growth of these materials in different applications
in analytical chemistry (Kole et al. 2011). Nanosorbents have been used in various
extraction techniques, such as solid phase extraction, dispersive solid phase extraction,
magnetic solid phase extraction, solid phase microextraction, dispersive μ-solid phase
extraction, and stir-bar sorptive extraction.
Metallic Nanoparticles
Metallic nanoparticles are metals that have at least one dimension (length, width, or
thickness) in the range of 1 to 100 nanometers. The basic characteristics of metallic
nanoparticles are their large surface areas, high surface energies, unique electronic
structures (due to the transition between molecular and metallic states), and a large
number of low-coordination sites, giving them the ability to store excess electrons.
Many metals are capable of forming nano-sized compounds; the most well-known of
these metals are gold, silver, and platinum. They have gained great attention as sorbents
because of their chemical stability and large surface areas, which increase the area
available for interactions. Gold nanoparticles are being used extensively in electronic
imaging, including scanning electron microscopy and transmission electron micros-
copy. Gold nanoparticles have been used extensively in bioanalysis because of their
great ability to selectively bind with compounds containing thiol and amino groups,
which can be absorbed simultaneously on the surface of gold nanoparticles to generate
well-organized and self-assembled monolayers (Hua et al. 2012).
Mixed Metal Oxide Nanoparticles
The unique electronic and magnetic properties of mixed metal oxide nanoparticles
include high surface area, high absorption capacity, and good chemical stability.
Because of these properties, these materials are of great importance in many areas of
chemistry, physics, materials science, and engineering. However, they have also
attracted attention for use as sorbents in the preparation of different samples. The
most common use of mixed metal oxide nanoparticles is for catalysis. Combining
two or more different metals in an oxide form can create new high-performance
materials for a number of different technological applications. In this union, metals
can act as an insulator; furthermore, their physical and chemical properties may
improve as a result of their interactions with other metals, thus improving the
performance of a nanostructured system. The close interactions and interfaces
between different materials with similar band potentials can improve charge sepa-
ration efficiency, increase charge carrier lifetime, and enhance charge transfer on a
microscopic scale Khajeh et al. (2013).
Magnetic nanoparticles are nanoparticle materials that consist of magnetic elements,
such as iron, nickel, cobalt, and their oxides. These materials are suitable for the
extraction of large biological molecules because of their good biocompatibility, large
surface area, ease of manipulation, ease of development of their surface with different
organic and inorganic groups, and simplicity of separation from a solution by magnetic
forces. Typically, the separation of magnetic nanoparticles is performed in several steps.

First, the magnetic nanoparticles are dispersed in the sample solution containing the
target analytes. In a short period of time, the maximum chemical equilibrium is
obtained, which is based on the partitioning of the analyte between a magnetic
nanoparticle’s solid and liquid phases. These particles can be suspended within the
sample solution for several hours, during which time they can selectively scavenge
dissolved species from the solution. By tailoring the size of the particles to specific
dimensions, they can be easily dispersed in an aqueous solution, without the need for
any mechanical or manual shaking. The particles can then be readily recovered,
together with the analytes, by magnetic forces. After washing out the contaminants,
the separated analytes can be eluted and used in further applications. Among all types of
magnetic nanoparticles, iron oxide nanoparticles (magnetite and maghemite) are the
most widely used in chemistry, physics, and materials science due to their ease of
preparation, low cost, high safety, and biocompatibility (Kole et al. 2011).
Solid-phase dispersion extraction with magnetic nanoparticles is an effective
means of determining many analytes in different environmental samples. The
approach has several advantages over other extraction techniques, such as liquid-
liquid extraction, solid-phase extraction cartridges, and solid-phase extraction disks.
Sample handling steps are minimized because the magnetic nanoparticle can be
mixed directly into the sample solutions without any additional treatment. Large
numbers of samples can be quickly and simultaneously treated, even in the sampling
field. Performing the dispersion in the field is very useful, especially when unstable
analytes are involved. When samples have to be transported from the field to the
laboratory, analytes may be lost through means such as degradation or volatilization.
Solid-phase dispersion, when applied in the field, limits or eliminates such losses.
Furthermore, carrying out this process in the field can reduce contamination of the
sample during transportation, storage, or in the laboratory environment. In addition,
the surface can be modified with various types of organic or inorganic groups to
increase their selectivity toward specific analytes. Moreover, it is possible to reuse
the magnetic nanoparticles for number of analytical cycles. One of the most impor-
tant physical advantages of this procedure is that less human and mechanical effort is
needed because no agitation is required. Even with a large number of samples and
large volume samples, magnetic nanoparticles move naturally through the sample by
Brownian motion and sedimentation, collecting the analytes. However, the adsorp-
tion capacity of these materials depends on a number of factors, such as the solution
pH, temperature, initial contaminant concentration, adsorbent dosage, and compet-
itive influence of interferences ions in the solution samples (Hua et al. 2012).
Carbon Nanomaterials
Carbon is the 14th element in the periodic table, with the symbol C and atomic
number 6. It is able to form different types of bonds with a number of atoms;
therefore, it has a number of exceptional physical, chemical, and biological proper-
ties. The application of carbon nanomaterials began when fluorine C60 was
discovered in 1985. Since then, researchers have been increasingly interested in

carbon nanomaterials. In a short period of time, their applications have become
numerous in chemistry, physics, and industry.
Carbon nanomaterials have a unique structure, with many outstanding physical
and chemical properties. Fluorine is a molecule of carbon with a polyhedral structure
consisting of five or six carbon rings. It can be synthesized in different forms: hollow
sphere, ellipsoid, tube, or many other shapes. Fluorine is a good acceptor of electrons
due to the lack of electronic density on its surface. Therefore, it can easily bind with
complexes containing electron donor groups. The main disadvantages of these
materials are their low solubility in aqueous solutions and organic solvents, high
price, and lower accessibility, which decreases their applicability.
Carbon nanotubes (CNTs) are one of the most widely used forms of carbon
nanomaterials. CNTs are graphite sheets that have been rolled up into small tubes.
Carbon nanotubes usually have an internal diameter of between a few tenths to tens of
nanometers, with a length of up to centimeters. Like fluorine, CNTs have low solubility
in aqueous and organic solutions, limiting their use. There are two basic types of carbon
nanotubes: single-walled carbon nanotubes (SWCNTs) and multiwalled carbon nano-
tube (MWCNTs). SWCNTs contain one sheet of cylindrical graphite, whereas
MWCNTs comprise two or more graphite sheets arranged around a central core.
Depending on their inner diameter and helicity, they may be metallic or semi-
conducting. Due to the unique mechanical, electrical, thermal, and magnetic properties
of CNTs, they have been used in many chemical, physical, and industrial fields. These
materials have gained importance as sorbents due to their high surface area, high ability
to form Л- Л interactions, relatively lower prices, wider accessibility, and ease of
functionalization with a variety of organic and inorganic groups (Wen et al. 2014).
Graphene and graphene oxide (G and GO) are other forms of CNTs, in which a
single layer of carbon atoms is held together by interfering with a number of Sp2
hybrid bonds. The unique characteristics of graphene arise from the presence of sp2
orbitals that form the Л state, which is positioned on the sheets of carbons that
consists of graphene. As a result, graphene is characterized by high hardness, very
high thermal conductivity, zero effective mass, and high charge carrier mobility,
while being visually transparent. Graphene has attracted attention as a good alter-
native to conventional sorbents due to its improved water dispersibility, high surface
area, high hardness, easy functionalization, and high purity. Graphene is also used in
the production of high-speed electronic devices, chemical sensors, and high-
efficiency chemical separation membranes. It can also be used to store hydrogen
for fuel-powered cells and water desalination. However, graphene is a superconduc-
tor with high oxidability and toxic qualities. Furthermore, even though it has no band
gap, it cannot be switched off (Tang et al. 2014).
Silicon-Based Nanomaterials
Silicon is a member of the group 14 in the periodic table of elements. The abundance
of silicon in nature makes it very inexpensive, allowing for a variety of silicon-
related applications. Silicon-based nanomaterials have amazing physical and chem-

ical properties compared to bulk silicon, including strong luminescence and stable
fluorescence. Silicon-based nanomaterials have been synthesized in different forms,
including silica dioxide nanoparticles (SiO2), core-shell layers, nanotubes, nano-
wires, nanorods, and nanoporous materials.
Silicon-based nanomaterials have improved properties in field emission, mechan-
ical, electrical, thermoelectrical, and catalytic activities. Because of these unique
properties, they have been used widely in semiconductors, photovoltaics, biomed-
ical, biological, and environmental analysis applications. They have been widely
used in the preparation of nanosorbents. Silicon nanosorbents are easy to synthesize
and modify. They have a variety of functional groups on their surface and are cheap,
non-toxic, and highly biocompatible (Namera et al. 2011) . Their core-shell form has
a large number of applications for the protection of various nanoparticles and the
grafting of many organic ligands. Their monolithic form is of great interest for online
extraction methods and separation of many analytes.
Polymeric Nanomaterials
Polymeric nanoparticles consist of nanoparticles distributed within the polymer or

copolymer matrix. These materials have been synthesized in different shapes,
including nanofibers, hollow nanofibers, core–shell nanofibers, nanorods, or nano-
tubes. Many forms of polymeric nanomaterials have been synthesized, including
organic, inorganic, and molecularly imprinted polymers. Organic polymer nano-
structures are among the most widely used sorbents in analytical chemistry. They
play an important role in sample preparation and pre-concentration processes. In this
sense, their low resistance to diffusion, large adsorption capacity, and rapid sorption
kinetics are the most distinguishing features of these materials, which increase their
ability to concentrate the analytes and increase their selectivity at the same time;
these characteristics are of fundamental importance in the trace analysis of both
organic and inorganic analytes in different complex samples.
Polymeric nanoparticles can be used as a template to insert inorganic nano-
materials as center-shell layers or supporting materials in the synthesis of different
nanomaterial structures. The use of organic polymers in the synthesis of nano-
materials has helped to develop their chemical composition, thermal, mechanical,
and sorption properties, as well as their biocompatibility. Applications for these
materials include homogeneous and heterogeneous catalysis, sensorics, filter appli-
cations, optoelectronics, active antimicrobial agents, and controlled drug delivery as
vehicles for therapeutics. Among them, conductive polymer nanofibers and nano-
films have gained considerable attention because of their high capacity for electro-
chemical synthesis (Bagheri and Saraji 2003).
Inorganic polymer-based nanoparticles such as xerogels, metal-organic frame-
works (MOFs), and core-shell layers have some important applications as sorbents.
Xerogels and aerogels (particularly, silica xerogels) have attracted some attention as
highly efficient sorbents because of their relatively high surface area, porosity, and
internal pore volume. Polysiloxanes are considered to be the most important inor-
ganic polymers in view of their commercial applications as an outside layer of
different extraction devices. Their applications range from medical uses and cos-
metics to water barriers. Polydimethylsiloxane is the most intensively used material
in sample preparation approaches. MOFs are characterized by the strong coordina-
tion bond between metal ions as nodes and organic linkers as rods. They also have a
very large surface area and their pores can vary greatly. Therefore, MOFs have been
widely used as a sorbents for the extraction of a large number of analytes, ranging
from very small ions to high-molecular-weight proteins (Moein et al. 2014).
Molecularly imprinted polymers (MIPs) are the third class of these materials.
They consist of ligands that are selectively bonded covalently or non-covalently to
synthetic polymers. MIPs allow the establishment of specific and selective linking
sites with the chemical and steric memory of a template. These synthetic biomimetic
receptors are widely used in analytical chemistry as sorbents because of their high
selectivity. Polymer-based nanomaterials have a number of features such as stability,
high selectivity, low cost, ease of preparation, flexibility of modification, and a wide
range of applications. Because of these unique features, MIPs have attracted interest
for extraction and separation in analytical chemistry. The preparation of these
materials requires three basic steps: polymerization, cross-linking with different
agents, and template removal. The preparation mechanism for polymer formation
can be a sol-gel process, free-radical polymerization (e.g., bulk, suspension, precip-
itation, or seed polymerization), or a condensation mechanism (Banerjee et al. 2015).
Magnetic Nanoparticles
Magnetic nanoparticles (MNPs) are metal oxide nanoparticles that can be controlled
using an external magnetic field. Their chemical, optical, electrical, thermal, and
magnetic properties are useful in different analytical steps, including the treatment of
the sample (extraction/clean-up and pre-concentration). Chromatographic separation
and detection contributed to the development of new analytical strategies and
improvements in conventional methods, therefore improving the performance of
analytical methods in terms of accuracy, precision, sensitivity, selectivity, detection
limit, speed, and cost (Wang et al. 2011).
Magnetic nanoparticles can be used in analytical chemistry in a variety of aspects,
such as direct use as sorbents without functionalization, incorporation with a
supporting material such as silica through chemical reactions, bonding to an inert
solid, and surface modification with organic, inorganic, or biochemical compounds
to specify their physical and chemical properties. Magnetic nanomaterials can be
synthesized from a large number of magnetic materials, such as iron, nickel, and
cobalt and their chemical compounds. Iron oxides (Fe2O3and Fe3O4) and their
derivatives (e.g., MnFe2O4 and CoFe2O4) are most commonly used for the prepara-
tion of magnetic nanomaterials because of their high magnetic properties, biological
suitability, and simplicity of their preparation compared to other magnetic materials
(Wang et al. 2015).
Due to the unique physiochemical properties of these materials, high flexibility in

their preparation and modification, and ease of use in the laboratory and field, they
have contributed significantly to improvements in various analytical strategies. The
use of MNPs can simplify the overall analytical steps. For example, the sorbent can
be dispersed in the sample solution directly instead of being backed into the
separation column. Furthermore, the separation rate can be improved from the
increased contact time between the sorbent surface and the sample. Finally, target
analytes can be loaded in the MNPs after extraction using a magnetic field, which is
easier than centrifugation or filtration. The significant benefits of using MNPs in
extraction are due to two main characteristics. First, the trend in the size of these
materials from micrometers to nanometers has resulted in increased extraction
efficiency. Secondly, flexibility in the chemical development of MNP surface has
helped to increase their selectivity. The typical steps for the use of MNPs in chemical
analysis are shown in Fig. 1 (Shen et al. 2011).
Separation using MNPs is carried out following some general steps. First, the
MNPs are dispersed into the sample solution containing the analyte and interfer-
ences. Then, the analyte is collected or interferences occur. Depending on the reason
for the sample preparation, one of two steps may happen next in the procedure. If the
target analyte must be pre-concentrated to increase sensitivity, the MNPs are corre-
lated with the target analyte; this union is achieved using an external magnetic field.
Then, the analyte is separated from the MNPs using appropriate solvents before the
magnet
dispersed isolated
Water sample
redispersed methanol
reuse (4 cycles)
HPLC-UV analysis
Fe3O4@SiO2@C16 analytes non target compounds
Fig. 1 The typical steps for the use of MNPs in chemical analysis
determination step. Conversely, if interferences must be removed from the sample

solution to clean-up the sample, they are retained on the surface of the MNPs and are
concentrated using a magnetic field. The remaining solution containing the target
analyte can be easily separated and the analyte can be detected.
Another promising area for MNPs in analytical applications is to improve
chromatographic and electrophoretic separation (Cao et al. 2015). In general,
MNPs behave as stationary or pseudostationary phases. The results obtained in
this case are better than conventional stationary-phase materials. Using MNPs, the
degree of resolution is significantly improved due to their high absorption capacity,
long lifetime, and attractive surface chemistry. MNPs are therefore typical materials
for use in a stationary or pseudostationary phase. On the other hand, because of the
small size of these materials (less than 100 nanometers), they can be backed into a
column at lower concentrations than conventional materials of stationary or
pseudostationary phases; thus, less than 1% of the total capillary volume would
be filled by MNPs. Moreover, these materials can be selectively associated with
capillary surfaces, the analytes, or both, resulting in high mass transfer and therefore
greatly changing the parameters of chromatographic separation. The large surface
area of MNPs also acts as a platform for the adsorption of analytes or ligands. Thus,
the precision and efficiency of separation can be improved (Ebrahimpour et al.
2015) .
Application of Nanomaterials as Sorbents for Environmental

Analysis
A comprehensive study of the literature on the applications for nanomaterials

indicates a level of interest in the use of these materials as sorbents for environmental
analysis. Researchers have used nanomaterials in sorbent technology to improve
extraction capacity, selectivity, and sensitivity, as well as to minimize the effect of
interferences. The possibility of synthesizing different types of nanomaterials with
different chemical and physical properties has allowed for wide analytical applica-
tions and new methods in this field, especially in terms of selectivity and sensitivity.
Recently, an increased number of studies have been published on the use of
nanomaterials as sorbents in sample treatment, chromatographic separation, and
derivatization-detection steps in different environmental samples. An examination
of these published works shows a common characteristic of all nanostructures that
improves extraction efficiency at all stages of analysis: their large surface area,
which facilitates the transfer of mass or interactions of the target analytes on the
surface of nanomaterials. Other favorable features include their adsorptive, mag-
netic, mechanical, electrical, thermal, optical, and catalytic properties, as well as
flexible surface modification. However, despite the positive addition of nanoparticles
to different extraction methods, a result trend is to develop new strategies involving
nanomaterials that improve enrichment ability, selectivity, detection limits, separa-
tion efficiency, and accessibility of suitable derivatization and detection systems
(Alberti et al. 2012).
Cross-References
▶ Magnetic and Nanostructural Properties of Cobalt–Zinc Ferrite for Environmental

Sensors
▶ Tailor-Made Molecular Traps for the Treatment of Environmental Samples
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Integrated Evaluation of Quantitative
Factors Related to the Environmental 45
Quality Scenario
Gustavo Marques da Costa, Annette Droste, Darlan Daniel Alves,

and Daniela Montanari Migliavacca Osório
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1118
Atmospheric Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1119
Particulate Matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1119
Polycyclic Aromatic Hydrocarbons (PAHs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1122
Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1122
Biomonitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1124
Characteristics of the Bioindicators Used to Evaluate the
Environmental Scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1124
Biomonitoring with Tradescantia pallida var. purpurea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1125
Biomonitoring with Ryegrass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1127
Monitoring of Atmospheric Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129
Particulate Matter Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129
Research Results: Quantitative Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1131
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1132
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1133
G. M. da Costa (*)
Programa de pós-graduação em Qualidade Ambiental, Universidade Feevale, Novo Hamburgo,
RS, Brazil
e-mail: markesdakosta@hotmail.com
A. Droste · D. D. Alves · D. M. M. Osório
Programa de pós-graduação em Qualidade Ambiental, Universidade Feevale, Novo Hamburgo,
RS, Brazil
e-mail: annette@feevale.br; darlandaniel@gmail.com; danielaosorio@feevale.br

https://doi.org/10.1007/978-3-319-73645-7_122
1118 G. M. da Costa et al.
Abstract
The emission of pollutants in the atmospheric air, originating from diffuse and
punctual sources, has generated the need for development and adaptation of
environmental quality assessment methods. In this chapter, the methods of
analysis for an integrated environmental quality assessment will be presented
using particulate matter, polycyclic aromatic hydrocarbons, metals, Tradescantia
pallida (Rose) D.R. Hunt. var. purpurea Boom, and Lolium multiflorum Lam.
Plants used as bioindicators show high sensitivity, or ability to accumulate
environmental pollutants and might, therefore, be used for the qualitative and
quantitative assessment of atmospheric air, indicating the risks of exposure of
organisms to pollutants. Indicator organisms are a tool of great importance to
diagnose the quality of ecosystems, besides contributing to the identification of
reference areas and critical areas in a certain region. The survey of meteorological
data and particulate matter are fundamental for the integrated evaluation of
atmospheric air quality, as well as the diagnosis of the environmental scenario.
Currently, a few studies have been carried out integrating different environmental
indicators for the evaluation of air quality. Chemical and biological indicators can
be used in environmental monitoring programs to assess the effects of atmo-
spheric pollutants on ecosystems, being able to provide data on short-, mid- and
long-term. Air monitoring data may assist public management by providing
reliable bases and methodologies for environmental control, supporting the
adoption of more restrictive environmental policies.
Keywords
Atmospheric air · Methods of analysis · Bioindicators · Monitoring programs
Introduction
The emission of pollutants in the atmospheric air from diffuse and punctual sources
has generated the need for development and adaptation of environmental quality
assessment methods, because air pollution can affect the climate and vegetation,
reduce visibility, and cause risks to human health (Gupta et al. 2007; Dallarosa et al.
2008; Brauer et al. 2008; Levy and Hanna 2011; Roberts 2013).
The main pollutants released into the atmosphere are carbon dioxide (CO2),
carbon monoxide (CO), sulfur oxides (SO2 and SO3) and nitrogen (NO2 and
NO2), ozone (O3), particulate matter (MP1, MP2.5 and MP10), volatile organic
compounds (VOCs), and polycyclic aromatic hydrocarbons (PAHs) (Meireles
et al. 2009; Alves et al. 2011).
In urban centers, the increase of the vehicular fleet leads to a lower capacity of
flow in the traffic, which results in a higher fuel combustion and consequent increase
of pollutants to the atmosphere (Crispim et al. 2012). The areas of intense vehicular
traffic accumulate complex compounds of pollutants with physicochemical charac-
teristics and varied toxicities (Carreras et al. 2013). These compounds may have
negative impacts on organisms and the environment due to the synergistic and
antagonistic effects of pollutants (Savóia et al. 2009).
45 Integrated Evaluation of Quantitative Factors Related to the. . . 1119
The identification and quantification of atmospheric pollutants can be performed

in two ways: (a) by use of equipment such as monitoring stations, active or passive
samplers; and (b) by active or passive biomonitoring (Álvares et al. 2002).
There are numerous models of air quality monitoring stations, capable of monitoring
and providing updated information at programmed intervals of the levels of one or more
pollutants at the same time, as well as data on the environmental meteorological
conditions, such as temperature, pressure, and speed and wind direction. Regarding
the sampling of the particulate matter (PM), it can be performed using dichotomous
samplers, which are capable of fractionating the particles into coarse and fine fractions.
Some plant species have a high sensitivity and/or ability to accumulate environ-
mental pollutants, such as heavy metals, polycyclic aromatic hydrocarbons (PAHs),
as well as genetic damages, which may be related to air pollution. Thus, these
organisms can indicate the risks of exposure to pollutants and are, therefore,
employed in the qualitative and quantitative assessment of air quality (Meireles
et al. 2009; Oliveira et al. 2012). Although the analysis of these pollutants and
damages in plants provide indirect information on the level of pollution, these
elements are not routinely measured by environmental agencies.
Active biomonitoring is a tool used to evaluate the air quality of environments
with different magnitudes of environmental impacts and consists of the systematic
analysis of the responses of organisms introduced in a standardized way in the
natural environment, for a certain period. It may also be passive, using naturally
occurring organisms in the monitored area (Markert 2007).
The combination of factors such as temperature, relative humidity, and precipitation
with atmospheric pollutants has been investigated on the response of exposed
bioindicators in supposedly polluted environments (Meireles et al. 2009; Savóia et al.
2009; Pereira et al. 2013). Biological indicators that show an integrated response to air
pollution with other environmental factors can be used as a complementary system to
monitor the effects of complex mixtures on living organisms (Savóia et al. 2009).
The integration of chemical and biological indicators can be employed in environ-
mental monitoring programs designed to evaluate the effects of atmospheric pollutants
on ecosystems and to provide data relating to short-, medium-, and long-term timescales.
However, at present, a few studies have been carried out integrating different environ-
mental indicators for the evaluation of air quality (Misík et al. 2011; Carreras et al. 2013;
Alves et al. 2015; Costa et al. 2016; Illi et al. 2017). In this chapter, methods of analysis
for an integrated environmental quality assessment will be presented using particulate
matter, polycyclic aromatic hydrocarbons, metals, Tradescantia pallida (Rose)
D.R. Hunt. var. purpurea Boom, and Lolium multiflorum Lam.
Atmospheric Pollutants
Particulate Matter
Particulate matter (PM) is considered to be the atmospheric particles that range in size
from a few nanometers (nm) to tens of micrometers (μm) in terms of aerodynamic
diameter. PM may arise from natural sources, such as wind-borne dust, sea spray, and
volcanoes, as well as from anthropogenic activities, such as combustion of fuels. PM is

removed from the atmosphere by two mechanisms: deposition at the Earth’s surface (dry
deposition), and incorporation into cloud droplets during the formation of precipitation
(wet deposition). The concentration and composition of PM vary greatly in the envi-
ronment, due to the climate action (wet and dry deposition) on its atmospheric residence
time, and also due to the geographic distribution of sources (Seinfeld and Pandis 2006).
Figure 1 shows some atmospheric particles collected in an urban area.
Depending on its sources, PM can be classified into primary and secondary
PM. Primary PM is released directly from its sources into the atmosphere and may
be originated from both anthropogenic and natural activities. The main anthropo-
genic sources of primary PM are construction, road traffic, stationary combustion
(mainly domestic coal burning), and industrial processes. Crust and sea can be listed
as the primary natural sources of primary PM, through the emissions of soil dust and
sea sprays, which are transported by the wind. Secondary PM is formed within the
atmosphere as a result of chemical reactions, producing substances of low volatility,
which consequently condense into solid or liquid phase, thereby becoming PM
(Fiordelisi et al. 2017; Kelly and Fussell 2012).
A significant fraction of the PM is anthropogenic in origin. The composition of
PM may contain transition metals, ionic species, organic compounds, carbonaceous
Fig. 1 (a) Particle of biological origin, (b) soot particle, (c) cubic-shaped particle, and (d) particle
characteristic of soil resuspension (above) and particle possibly originated from anthropogenic
sources (below) (Source: Adapted from Alves et al. (2015)
materials, minerals, reactive gases, and materials of biologic origin. The carbona-
ceous fraction consists of both elemental and organic carbon. Elemental carbon, also
called black carbon, graphitic carbon, or soot, is emitted directly into the atmosphere,
predominantly from combustion processes. Particulate organic carbon is emitted
directly by sources or can result from the atmospheric condensation of low-volatile
organic gases (Fiordelisi et al. 2017; Seinfeld and Pandis 2006).
Particles of aerodynamic diameter less than 10 μm (PM10) have been widely studied in
recent years in its coarse (PM2.5–10), fine (PM2.5) fractions, due to their potential impacts
on health, environment, visibility, and climate (Cheung et al. 2005; Harrison and Yin
2000; Tai et al. 2010). Particles of aerodynamic diameter larger than 10 μm are filtered
through the nose, but they are too large to reach the respiratory tract. Thus, these particles
can be trapped in the mucus lining within the nose and can be easily eliminated through
normal breathing activities (Fiordelisi et al. 2017). On the other hand, PM10 can reach the
lungs and be deposited in the nasal cavities and upper airways through nasal breathing.
The fine fraction may penetrate deeper into the lungs and be deposited in alveolar regions
during mouth breathing, and can also be absorbed into the bloodstream through alveolar
capillaries. The fine fraction may cause a variety of health problems, such as (a) premature
death in people with heart or lung disease, (b) nonfatal heart attacks, (c) irregular heartbeat,
(d) aggravate asthma, (e) decreased lung function, and (f) increase respiratory symptoms,
such as irritation of the airways, coughing, or difficulty breathing (EPA 2017).
The fine and coarse fractions, in general, originate separately, are transformed
separately, are removed from the atmosphere by different mechanisms, show differ-
ent chemical composition and optical properties, and differ significantly in their
deposition patterns in the respiratory tract. Therefore, the distinction between fine
and coarse PM is a fundamental one in any discussion regarding their physical and
chemical properties, measurement techniques, and environmental and health effects
(Seinfeld and Pandis 2006).
The main sources of PM can be summarized as follows: (a) vehicular traffic,
(b) industry, (c) domestic fuel burning, (d) natural sources, and (e) unspecified anthro-
pogenic sources. Vehicular traffic originates different kinds of emissions, especially due
to the different types fuels used (diesel, gasoline, alcohol, etc). In addition to primary
PM, emissions from vehicles exhaust and emissions of organic and inorganic gaseous
PM precursors from the combustion of fuels and lubricants, vehicles emit significant
amounts of particles through the wear of brake linings, clutch, and tires (Gietl et al. 2010;
Karagulian et al. 2015; Thorpe and Harrison 2008). For instance, Gietl et al. (2010)
suggest that barium (Ba) could be used as a feasible quantitative marker for brake dust in
the urban air, from which airborne concentrations of brake dust can be estimated. This
assumption is based on the similarity between the particle size distribution Ba in the
roadside air and urban background air, which is strongly suggestive that the brake dust
should be the predominant source of Ba in the urban background air. Industry is a
heterogeneous source and includes mainly emissions from oil combustion, coal burning
in power plants, and emissions from different types of activities (petrochemical, meta-
llurgic, ceramic, pharmaceutical, etc.). Industrial sources are sometimes mixed with
unidentified combustion sources or road traffic (Belis et al. 2013; Karagulian et al.
2015). Domestic fuel burning includes wood, coal, and gas fuel for cooking or heating.
A typical case of household air pollution by coal burning for domestic heating is found
in Central Europe, where wood and coal are used for domestic heating. Natural sources
of particulate matter are basically represented by marine and crustal emissions, which
enter the atmosphere through the resuspension of soil dust and the marine sprays, both
carried by the windblown. Soil dust is characterized by elements abundant in the Earth’s
crust rocks and soil, while the marine sprays are mostly characterized by sea salt
particles, especially NaCl (Seinfeld and Pandis 2006). Unspecified anthropogenic
sources mainly include secondary particles formed from unspecified pollution sources
of anthropogenic origin. Primary particle emissions include mechanically generated
particles and primary carbonaceous particles, as well as carbonaceous fly-ash particles
produced from high-temperature combustion of fossil fuels in coal power plants
(Karagulian et al. 2015).
Polycyclic Aromatic Hydrocarbons (PAHs)
PAHs were one of the first atmospheric species to be identified as being carcino-
genic. Formed during the incomplete combustion of organic matter, i.e., coal, oil,
wood, and gasoline fuel, PAHs consist of two or more fused benzene rings in linear,
angular, or cluster arrangements and, by definition, they contain only carbon and
hydrogen (Seinfeld and Pandis 2006).
These chemical species have low solubility in water, low vapor pressure, and high
melting and boiling points. They are solid at ambient temperature and can range
from semivolatile molecules to molecules with high boiling points. The composition
profiles of these mixtures vary according to the generation process.
PAHs observed in the atmosphere range from bicyclic species such as naphtha-
lene, present mainly in the gas phase, to PAHs containing seven or more fused rings,
such as coronene, which are present exclusively in the aerosol phase. Intermediate
PAHs such as pyrene and anthracene are distributed in both the gas and aerosol
phases (Seinfeld and Pandis 2006).
The recognition of the harmful effects of these pollutants on plants has led to several
studies in potentially compromised areas in relation to air quality (Klumpp 2004;
Sandrin et al. 2013; Illi et al. 2017). The importance of identifying PAHs is related to
their carcinogenic and/or mutagenic potential. The following PAHs (Fig. 2) are classi-
fied as carcinogenic by the International Agency for Research on Cancer (IARC).
The HPAs can be found in the atmosphere in the form of gases and MP. The
highly industrialized and urbanized areas are considered the major contributors of
these compounds, due to the emissions originated from industrial activities and from
fossil fuel combustion by motor vehicles (Zhang and Tao 2009).
Metals
Metals are naturally occurring constituents in the environment and cannot be

degraded or destroyed, being persistent everywhere, varying in terms of types and
45
2 12 1 2 11 2
1 3 1 3 10 12 1 3
11 2
11 12 10 12 4
4 3 9
10 9 11 5 4
4
9 5 8 10 6 8 5
5
8 7 6 6 9 8 7 7 6
7
Benz[a]anthracene Chrysene Benzo[b]fluoranthene Benzo[ j]fluoranthene
2 2
12 1 1 3 1 3 12 1
11 2 12 13 14 11 2
4
10 11 4 12 10
3
9 9 3
10 5 5
11
8 4 9 7 6 8 4
7 6 5 8 6 10 8 7 6 5
Integrated Evaluation of Quantitative Factors Related to the. . .
7 9
Benzo[a]pyrene Benzo[e]pyrene Dibenz[a,h]anthracene Indeno[1,2,3-cd]pyrene
Fig. 2 Carcinogenic PAHs Adapted from IARC (2010)

1123
concentrations from site to site. In addition, some metals are essential for
maintaining proper health of humans, animals, plants, and microorganisms. How-
ever, human activities alter the natural geological and biological redistribution, as
well as the chemical form of metals released to the environment, through the
extraction marketable metals from the soil and emission of metals to air, water,
and also back to the soil. Because the toxicokinetics and toxicodynamics of metals
depend on the metal type and also on the form of the metal or metal compound, the
ability of the receptor organisms is to regulate and/or store metals, such alterations
often affect the metals toxicity by allowing them to bioaccumulate in plants and
animals, bioconcentrate in the food chain, or attack specific organs of the body.
Monitoring and controlling of metals in the atmosphere are thus critical for reducing
exposure pathways and protecting human health and the environment (EPA 2007;
EPA 2010).
Metals are emitted into the atmosphere by numerous sources, such as road dust,
construction activities, motor vehicles, coal and oil combustion, incineration, and
other industrial activities (Yadav and Satsangi 2013). A number of studies have been
carried out to assess the fate and behavior of various heavy metals in the environ-
ment, as well as their environmental effects. Cd, Pb, and Hg have been given a
particular attention in these studies (WHO 2007; Pacyna et al. 2009). The heavy
metals Cd, Pb, and Hg are common air pollutants, being emitted mainly as a result of
various industrial activities. Although the atmospheric levels are low, they contribute
to the deposition and build-up in soils.
Long-term exposure to Cd, both environmental and occupational, may cause
severe damage to the kidney and bone. Cd induces renal function impairment,
which is reflected by increased urinary excretion of low molecular weight proteins.
Another effect of cadmium toxicity is reduced bone density resulting from prolonged
exposure (Trzcinka-Ochocka et al. 2010).
Pb is one of the most hazardous heavy metals due to its toxic effects on the
environment and on human health. Epidemiologic studies have shown that even at
low exposure levels, chronic exposure to lead in humans may result in adverse
effects on the blood and on the central nervous system (Li et al. 2012).
Hg is also toxic in the elemental and inorganic forms, but the main concern is
associated with the organic compounds, especially methylmercury, that accumulate
in the foodchain, i.e., in predatory fish in lakes and seas, as these are the main routes
of human exposure.
Biomonitoring
Characteristics of the Bioindicators Used to Evaluate

the Environmental Scenario
Bioindicators are organisms that react to environmental changes by modifying their

vital functions, and/or their chemical composition, providing information about the
environmental scenario. A bioindicator should be taxonomically defined and easily
Fig. 3 Cuttings of
Tradescantia pallida var.
purpurea with inflorescences
protected by two bracts.
recognizable by nonspecialists, be broadly geographically distributed, be abundant

or easy to collect, have known ecological characteristics, and be usable in laboratory
studies (Markert 2007).
Considering that plants are generally more sensitive than animals, they have a
faster developmental stage and reproductive cycle; being able to respond to envi-
ronmental conditions in a short period of time, they have preferred bioindicator
attributes when compared to animals (Alves 2001).
Bioindicators are a tool of great importance to diagnose the quality of ecosystems,
besides contributing to the identification of reference areas, and critical areas in a
given region (Merlo et al. 2011). Depending on the environment and what is being
monitored, the use of active bioindicators is considered more advantageous, since
some factors can be previously established or standardized, which contributes to the
fidelity of interpretation of the results (Guimarães et al. 2000).
Tradescantia is one of the most used and validated indicators of genetic damage
caused by air and water pollutants (Ma et al. 1994; Klumpp et al. 2006; Thewes et al.
2011; Costa et al. 2016). Tradescantia pallida (Rose) D.R. Hunt. var. purpurea
Boom, a species well adapted to the tropical and subtropical climate, has been used
in studies of air genotoxicity in Brazil (Meireles et al. 2009; Savóia et al. 2009; Costa
and Droste 2012; Pereira et al. 2013). This species has an herbaceous bearing with
approximately 25 cm of height, lance-shaped leaves, inflorescence protected by two
bracts, blooms the whole year (Fig. 3). Its special advantage is the fact that flower
buds can be used to evaluate the genotoxic potential of atmospheric air and water
bodies (Thewes et al. 2011; Costa and Droste 2012; Costa et al. 2014; Cassanego
et al. 2014, 2015; Kieling-Rubio et al. 2015).
Biomonitoring with Tradescantia pallida var. purpurea
The micronucleus bioassay in Tradescantia L. (Trad-MCN bioassay) is based on the

micronucleus count (MCN) (Fig. 4) formed in pollen grains and visualized in the
Fig. 4 Tetrad with cells

presenting micronuclei
stage of tetrad resulting from the meiotic process, which presents high sensitivity to
genotoxic agents (Ma 1982). Micronuclei are derived from whole chromosomes or
chromosome fragments. They are unable to attach to a spindle fiber or due to
defective cell division (Lindberg et al. 2007). A structure considered MCN should
have a diameter less than one-third of the nucleus, be separate, and has similar
coloration to it (Grisolia 2002). In the meiotic division, the chromosomes are more
sensitive to the breakdown than mitotic chromosomes, especially in prophase I,
during pachytene and diplotene, which increases the sensitivity of the bioassay
(Ma 1982).
The genotoxic effects observed in Tradescantia cannot be extrapolated to
humans; however, it is acceptable to assume that if a pollutant does not cause
detectable damage to sensitive species, it will not affect any other species, including
humans (Guimarães et al. 2000).
Specifically, when it comes to atmospheric air assessment, as living organisms
respond to different abiotic factors, it is important to investigate whether the genetic
damage recorded in T. pallida var. purpurea also come from meteorological vari-
ables. Therefore, the combination of factors such as temperature, relative air humid-
ity, and precipitation with atmospheric pollutants has been investigated on the
response of Tradescantia var. purpurea (Meireles et al. 2009). Biological indicators
that show an integrated response to air pollution with other environmental factors
can be used as a complementary system to monitor the effects of complex mixtures
on living organisms (Savóia et al. 2009).
The plants of Tradescantia pallida var. purpurea need to be grown in plastic
vessels (37 cm 20 cm 20 cm) containing 4 kg of commercial soil watered three
times a week and still monthly applied 100 mL of fertilizer N: P: K (nitrogen:
phosphorus: potassium) in the proportion of 10:10:10 (Thewes et al. 2011). For each
bioassay performed, twenty cuttings (15 cm length), with flower bud stage inflores-
cences, one of each plant, must be partially immersed in containers containing 2 L of
distilled water, and remain for 24 h for adaptation under controlled conditions in the
laboratory at the temperature of 26 1 C (Cassanego et al. 2014).
In order to perform the bioassay, it is necessary to standardize the experimental
conditions, such as the use of the period of adaptation and recovery of T. pallida
var. purpurea in distilled water. This fact ensures that the cellular damages
observed are only related to the genotoxic agents present in the atmospheric
environment exposure. Among other criteria, the following should be highlighted:
(a) avoid exposure of the buds on days with extreme temperatures; (b) not to
expose the plant on rainy days; (c) irrigate the live collection weekly to ensure
good hydration conditions for plants and avoid water stress; and (d) renovate the
soil to avoid nutrient shortage.
The inflorescences with flower buds need to be fixed in absolute ethanol: glacial
acetic acid (3:1 v:v) and, after 24 h, be transferred to 70% ethanol and kept under
refrigeration at 4 C. For each sample, 300 tetrads per slide should be observed by
optical microscopy, 400 times increase, and the number of MCNs recorded (Thewes
et al. 2011). Micronucleus frequencies are calculated and expressed in terms of
MCN/100 tetrad (Ma et al. 1994).
Biomonitoring with Ryegrass
Lolium multiflorum Lam (Fig. 5) is another bioindicator of atmospheric pollution,

mainly in relation to the accumulation of sulfur and metallic elements (Klumpp
2004; Alves et al. 2015). It has recently been used to understand the spatial
distribution, and the impacts of metals and polycyclic aromatic hydrocarbons
(PAHs) on the atmosphere (Lehndorff and Schwark 2004; Lendorff and Schwark
2009; Ratola et al. 2010; De Nicola et al. 2011).
The ryegrass L. multiflorum can be cultivated in plastic vases with a standard-
ized substrate, which may be Carolina Soil type (Illi et al. 2017) or the commercial
Fig. 5 Lolium multiflorum

Lam under cultivation
Eucatex Plantmax SFA substrate mixed with vermiculite (3:1, v/v) (Pasqualetti
et al. 2015; Sandrin et al. 2013). The amount of seed may range from 0.3 g
(Illi et al. 2017) to 0.8 g (Pasqualetti et al. 2015, Sandrin et al. 2013). The exposure
time varies from 28 to 30 days. Figure 6 shows the main steps in the use of ryegrass
as bioindicator.
For the analysis of metallic elements, the ryegrass leaves should be dried in a
laboratory stove at 70 C. After drying, they should be ground in a porcelain mortar
using a pestle, weighed and digested with a nitric acid solution in a microwave oven.
The quantification of the metals can be accomplished by flame atomic absorption
spectroscopy (FAAS), graphite furnace atomic absorption spectroscopy (GFAAS),
or inductively coupled plasma mass spectrometry (ICP-MS) (Klumpp 2004).
The gas chromatography coupled to mass spectrometry (GC/MS) technique can
be used for the determination of PAHs in ryegrass. The methodology for sample
preparation and extraction is shown in Fig. 7. The ryegrass leaves should be cut at
4 cm above the substrate, and approximately 5 g of leaves should be weighed for the
extraction, using the Soxhlet extraction method.
The samples are extracted with approximately 250 mL of dichloromethane
(CH2 Cl2) for 24 h at 45 C. After this process, the extracts are separated/pre-
concentrated using the clean-up procedure in a silica-gel column (activated with
5% distilled water). This extraction procedure is based on Teixeira et al. (2011) and
was optimized from USEPA TO 13A (USEPA 1999).
After the quantification step, reference patterns should be searched for the sub-
stances that have been quantified. For metals, the classification described by Klumpp
(2004) in the biomonitoring of several European cities (EuroBionet), which has
reference values for Cd, Pb, Cr, Ni, Cu, Zn, Fe, and V, in the L. multiflorum species is
normally used. This classification is divided into four levels of atmospheric pollu-
tion, according to the concentration of metals: class 1 (very low), class 2 (low), class
0.60 g of 3 days
seeds exposure
15 days
germination in
a suitable site
1.5 m
Standardized
substrate
Fig. 6 Methodology of cultivation and exposure of L. multiflorum for analysis of PAHs and
metals
Fig. 7 Sample preparation and sample extraction from L. multiflorum for PAHs analysis
Table 1 Classification mentioned by Klumpp (2004)

Cd Pb Cr Ni Cu Zn Fe V
Class 1 – Very low ≤0.04 ≤0.8 ≤0.8 ≤5.5 ≤7.1 ≤31.7 ≤180 ≤0.32
Class 2 – Low 0.05– 0.9– 0.9– 5.6– 7.2– 31.8– 181– 0.33–
0.07 1.6 1.5 9.3 11.6 45.1 309 0.49
Class 3 – High 0.08– 1.7– 1.6– 9.4– 11.7– 45.2– 310– 0.50–
0.10 2.4 2.3 13.1 16 58.6 438 0.65
Class 4 – Very high >0.10 >2.4 >2.3 >13.1 >16.0 >58.6 >438 >0.65
3 (high), and class 4 (very high), as shown by Table 1. With respect to PAHs, the
results are usually compared with those of other studies that monitored these
pollutants in similar areas. Table 2 presents studies with Lolium sp.
Monitoring of Atmospheric Pollutants
Particulate Matter Sampling
MP can be sampled using dichotomous samplers, which are devices capable of

segregating the PM into coarse and fine fractions (Fig. 8). The dichotomous samplers
are generally equipped with atmospheric pressure and temperature sensors, to allow
it to control the volumetric inflow rate, as well as a computer, for control of the
system and storage of data. The air sample enters a fractionating inlet, usually at a
flow rate of 1 m3 h1, i.e., 16.7 L min1. Due to the axial symmetry shape of the
inlet, the sampling efficiency is independent of wind direction. A coarse screen
Table 2 Studies with Lolium sp.

Site Species Evaluated pollutants Reference
Cubatão region, Brazil Lolium Fluor, sulfur Klumpp
multiflorum et al.
italieum cv. Lema (1994)
Edinburgh, Sheffield, Italian rye grass Sulfur, Fe, Cu, Zn, Pb, Cd, Klumpp
Copenhagen, Düsseldorf, (Lolium Cr, Ni, Sb, As, and V (2004)
Nancy, Hohenheim, multiflorum
Klagenfurt, Lyon, Verona, “Lema”)
Barcelona, Valencia,
Europe
Galicia, Spain Lolium perenne Fluoride Rey-
Asensio
and
Carballeira
(2007)
Cubatão, Brazil Lolium Naphthalene, acenaphthene, Rinaldi
multiflorum‘Lema fluorene, phenanthrene, et al.
anthracene, fluoranthene, (2012)
pyrene, benzo[a]anthracene,
chrysene, benzo[b]
fluoranthene, benzo[k]
fluoranthene and benzo[a]
pyrene.
São Paulo, Brazil L. multiflorum Fructose Sandrin
Lam. sp. italicum et al.
Beck cv. Lema (2013)
Sinos River basin, Southern Lolium Al, Ba, Cd, Cu, Pb, Cr, Fe, Alves et al.
Brazil multiflorum Mn, Ni, and Zn (2015)
sp. italicum
cv. Lema.
Tropical areas of Southeast Lolium N, S, Mg, Fe, Mn, Cu Bulbovas
Brazil, South America multiflorum and Zn et al.
(2015)
Southern of Brazil, South Lolium Al, Ba, Cd, Cu, Pb, Cr, Fe, Illi et al.
America multiflorum Mn, Ni, and Zn (2017)
sp. italicum
cv. Lema.
prevents the drag of large particles and insects. Thus, the particles smaller than
10 μm pass through an inlet tube, which serves to straighten the flow, and then, into
the virtual impactor.
The virtual impactor is the basis for the operation of a dichotomous sampler. The
sample flow entering the virtual impactor is split into two separate flow systems.
Particles are accelerated through a nozzle and enter the fractionation zone. Due to the
geometry of the acceleration nozzle, only 10% of the total flow, which enters the
impactor (100 L h1), goes through the collection nozzle. Particles larger than
2.5 μm (PM2.5–10) are drawn directly into the collection nozzle, due to their greater
PM10 inlet
Virtual impactor
PM2.5 PM2.5-10
Mass Flow Controller
Flow 900 L h−1 Flow 100 L h−1

Pump
Filter holder
Exhaust
Temperature measurement
Fig. 8 General flow scheme of a dichotomous sampler (Source: Adapted from MCZ 2017)
inertia. These particles “impact” into the low flow region of the collection tube and
then deposited onto a membrane filter. The remaining 90% of the flow (900 L h1),
which contains the smaller particles (PM2.5), passes around the nozzle and through a
tube, and the particles are collected in a separate membrane filter (MCZ 2017).
Research Results: Quantitative Factors
A study conducted by Alves et al. (2015) in the lower part of the Sinos River basin
(SRB), Southern Brazil, between October 2013 and March 2014, assessed the air
quality through the determination of the concentrations of MP2,5-10, MP2.5 and the
metallic elements Al, Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn, and Hg in the leaf area of
the Lolium multiflorum. The mean concentrations of MP2.5–10 and MP2.5 were 9.1 μg
m3 and 4.7 μg m3. The concentrations of metallic elements, especially Pb, Cr, and
Zn, resulted in Class 4 (very high pollution levels), according to the classification
proposed by Klumpp (2004).
Atmospheric air genotoxicity studies conducted in urban areas in Caraá, Taquara,
Campo Bom, São Leopoldo, Esteio, and Canoas districts located in southern of
Brazil and in riparian forest environments in Caraá, Taquara, and Campo Bom in the
upper, middle, and lower stretches of the SRB evidenced that the flower buds of
T. pallida var. purpurea exposed to urban areas presented MCN frequencies ranging
from 2.37 to 5.44; the lowest frequency in the municipality of Caraá, located in the
upper stretch of the SRB, and the highest in Canoas, in the lower stretch. In the
environments of riparian forest, the MCN frequencies ranged from 1.92 to 3.38, with
the highest average in the municipality of Taquara, located in the middle stretch of
the SRB. The lower MCN frequencies recorded for Caraá may be related to the good
state of conservation of the vegetation and the low urbanization in the upper stretch
of the SRB. High urbanization and industrialization, as well as the intense vehicular
traffic, contribute to the increase of potentially genotoxic atmospheric pollutants.
High MCN frequencies in Tradescantia pallida var. purpurea have also been
reported in other studies in the SRB. Costa and Droste (2012) observed MCN
frequencies ranging from 1.03 to 8.13 in plants exposed in a rural area of the
municipality of Novo Hamburgo and in an urban area in the municipality of Estância
Velha. Blume et al. (2014) observed MCN frequencies ranging from 4.77 to 8.28 at
an urban area of the municipality of Sapucaia do Sul. Cassanego et al. (2015)
recorded MCN frequencies ranging from 2.13 to 7.23 in urban areas and from
1.50 to 4.80 in riparian forest environments, located in the upper, middle, and
lower stretches of the SRB.
These MCN frequencies were caused by pollutants present in the environments
monitored. However, it is not possible to relate the results of the MCN frequency
with any specific compound, due to the complex mixture of pollutants present in the
atmosphere emitted from vehicular traffic and industry. Heavy vehicles, like buses
and trucks, are responsible for most of the sulfur and nitrogen oxide emissions
(Santos et al. 2015), while light vehicles and mixed-use vehicles, gasoline and
alcohol-powered, are the main producers of carbon monoxide and hydrocarbons
(Teixeira et al. 2008).
Air quality monitoring studies carried out in the municipalities of Canoas, Esteio,
and Sapucaia do Sul, in the lower stretch of the SRB revealed the presence of CO,
SO2, NOx, PAHs, and PM, which were attributed to vehicle emissions and to
industrial processes (Migliavacca et al. 2012; Teixeira et al. 2012). In metropolitan
regions with a high incidence of traffic congestion, about 90% of CO emissions
come from the burning of fossil fuels by motor vehicles (Teixeira et al. 2008).
In addition, studies showed that stressing meteorological conditions might influence
the response of the Tradescantia pallida var. purpurea (Savóia et al. 2009; Pereira et al.
2013; Spósito et al. 2015), since the low relative air humidity and high temperatures
seem to stimulate the opening of the stomata, thus increasing the absorption and
transportation of genotoxic substances to the target cells (Klumpp 2004).
Conclusion
An air quality monitoring program that integrates biomonitoring and conventional

monitoring techniques of key parameters, such as MP, metallic elements, and PAHs,
and that integrates the data obtained from these techniques, is able to provide
sufficiently robust conclusions regarding the air quality of an area of interest, such
as, for instance, a large urban center. The results obtained from the monitoring of
several points, located in strategic sites, allow the definition of priority areas, in
terms of atmospheric pollution, for which, specific actions can be taken, aiming to
reduce the environmental impacts caused by air pollution.
The bioassays presented in this chapter can provide information on the areas of
risk and also allow a record of the effects of complex mixtures of pollutants on living
organisms. The survey of meteorological data, vehicular traffic, and the profile of the
industries are also fundamental to verify a possible relation with the response
provided by the bioindicators.
Considering that the bioindication methods are important tools for the assessment
of particular conditions of each environment, the implementation of bioassays as a
technique for the management and control of atmospheric pollution is suggested to
the public agencies, especially in regions influenced by pollution sources from
different nature, with different profiles.
Therefore, to carry out an air quality assessment, it is necessary to use methods
capable of integrating variables, which are representative of the environmental
conditions of the evaluated region. Air monitoring data may assist public manage-
ment by providing reliable bases and methodologies for environmental control,
supporting the adoption of more restrictive environmental policies.
Cross-References
▶ Air Pollution
▶ Monitoring and Risk Analysis of PAHS in the Environment
Acknowledgments The authors thank Larissa Meincke for the edition of Figures 6 and 7.
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Characterizing the Cell Surface Properties
of Hydrocarbon-Degrading Bacterial 46
Hamid M. Pouran, Steve A. Banwart, and Maria Romero-Gonzalez
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1141
Experimental Section and Sphingomonas spp., Sph2 Case Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1142
Sph2 Growth Condition, and Preparation for Infrared Spectroscopy of Its
Cell Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1143
Potentiometric Titration of Sph2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1143
Modelling Surface Protonation of Sph2 Based on the Titration Data . . . . . . . . . . . . . . . . . . . . . 1144
Zeta Potential Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1145
Sph2 Biofilm Formation on Hematite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1146
Results and Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1146
Infrared Spectroscopy of Sph2 Cell Wall . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1146
Sph2 Surface Potential in Different Ionic Strengths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1146
Sph2 Potentiometric Titration and the Data Optimization Using ProtoFit . . . . . . . . . . . . . . . . 1148
Sph2 Biofilm Formation on the Hematite Surface Under Different Ionic Strengths . . . . . . 1154
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1155
Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1157
Preparing the Hematite Surface for Cell Adhesion Studies (Synthesis, Coating,
and Characterization) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1157
Bacterial Strains, Growth Conditions, and Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . 1158
Biofilm Formation Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1158
Glycosphingolipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1161
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1164
H. M. Pouran (*)
Faculty of Science and Engineering, University of Wolverhampton, Wolverhampton, UK
e-mail: hamidpouran@gmail.com
S. A. Banwart
School of Earth and Environment, University of Leeds, Leeds, UK
M. Romero-Gonzalez
Department of Geography, University of Sheffield, Sheffield, UK

https://doi.org/10.1007/978-3-319-73645-7_131
1140 H. M. Pouran et al.
Abstract
This chapter describes some of the most common methods used to characterize
the cell surface properties of the bacterial cells. As a case study, the focus of this
chapter is on Sphingomonas spp., Sph2, which is a Gram negative and hydro-
philic bacterial strain. The species used in this research was isolated from
groundwater at a phenol-contaminated site. This hydrocarbon-degrading strain
that can participate in bioremediation of polluted environments belongs to
Sphingomonadaceae family. This group of bacteria is unique among Gram-
negative cells because of having glycosphingolipids (GSL) instead of the lipo-
polysaccharide (LPS) layer in their cell wall. To characterize this strain, its surface
properties were examined using potentiometric titration, modelling surface pro-
tonation sites using ProtoFit, zeta potential measurements, and attenuated total
reflection Fourier-transform infrared (ATR-FTIR) spectroscopy. There is no
published detailed study about cell wall characteristics of Sph2 yet, and this
research reports such information for the first time. In addition, to investigate
effects of the solution ionic strength on Sph2 adhesion behavior on metal oxides,
its biofilm formation on hematite, as the model mineral, was evaluated in three
different ionic strengths; 200 mM, 100 mM, and 20 mM. The ATR-FTIR
analysis showed that despite the unique cell wall chemistry of Sph2 among the
Gram-negative strains, its surface functional groups are similar to other bacterial
species. Hydroxyl, carboxyl, phosphoryl, and amide groups were detected in
Sph2 infrared spectra. The potentiometric titration results showed that Sph2
PZC is approximately 4.3. Optimizing the titration data based on ProtoFit
non-electrostatic model (NEM) provided compatible results to the infrared spec-
troscopy analysis and four pKa values were identified; 3.9 0.3, 5.9 0.2,
8.9 0.0, and 10.2 0.1, which could be assigned to carboxyl, phosphate,
amine, and hydroxyl groups, respectively. Zeta potential measurements
46 Characterizing the Cell Surface Properties of Hydrocarbon-Degrading. . . 1141
demonstrated that changing the ionic strength from 200 mM to 20 mM shifts

the zeta potential by 20 mV. Direct observation showed that this alteration in
the ionic strength coincides with a tenfold increase in the number of Sph2
attached cells to the hematite surface. This could be attributed to both electrostatic
interactions between the cell and surface, and conformational changes of Sph2
surface biopolymers. In addition to reporting Sph2 cell wall characterization
results for the first time, this study highlights importance of ionic strength in
the cell adhesion to the mineral surfaces, which directly influence biofilm forma-
tion, bioremediation, and bacterial transport in aqueous systems.
Keywords
Sphingomonas spp. · Attenuated total reflection Fourier-transform infrared
spectroscopy (ATR-FTIR) · Potentiometric titration · Biofilm formation · Cell
surface · Cell wall chemistry · Hematite · Electrostatic interactions · Ionic
strength · Biopolymers · Solution chemistry · Attached growth · Interface
interactions · ProtoFit
Introduction
Bioremediation or clean-up of hydrocarbon contaminated sites relying on the indig-

enous microorganisms (e.g., bacteria) is a cost effective and environmental-friendly
approach. In this method, the indigenous bacteria play the dominant role and convert
the contaminants to harmless/less harmful products (Gutman et al. 2014; Pouran
et al. 2008, 2014; Ojeda et al. 2008). Bacterial cells, despite their small size, are
dynamic (e.g., using different sources of carbon and energy) and capable of adapting
to different environmental conditions (O’Toole et al. 2000; O’Toole and Wong
2016). Their lifestyle includes both planktonic and attached forms. Cell attachment,
which is followed by biofilm formation, is the prevailing bacterial form (Pouran et al.
2017). It is well established that the bacterial life style and its physiological prop-
erties directly influence the biodegradation rate (Andrews et al. 2010).
To design better bioremediation processes, and predict attenuation of the con-
taminants in the affected sites, deeper knowledge of the bacterial cells behaviors in
natural environments, particularly biofilm formation, is essential. Sphingomonas is a
metabolically versatile bacterial strain and capable of participating in bioremediation
of contaminated environments (Chen et al. 2008; Gabriel et al. 2005a, b). For
example, we know that Sphingomonas xenophaga Bayram, isolated from the acti-
vated sludge of a municipal wastewater treatment plant, can degrade nonylphenol
mixtures by utilizing these as a sole carbon and energy source (Gabriel et al. 2005a).
In our previous publications, we evaluated biofilm formation of different bacterial
strains, isolated from contaminated soils and aquifers, on iron oxide surfaces. Effects
of these minerals’ hydrophobicity and pH-dependent surface charge on the attached
growth of Rhodococcus spp. (RC92 & RC291), Pseudomonas spp. (Pse1 & Pse2), and
Sphingomonas spp. (Sph1 & Sph2) were studied in this research (Pouran et al. 2009,
2014, 2017; Andrews et al. 2010; Geoghegan et al. 2008). Among these genetically
diverse strains, Sphingomonas spp., Sph2, a hydrophilic strain with negative surface
charge in the experimental conditions (pH 6.5), showed attachment behavior
anomalies contrary to the expected electrostatic attractions between the minerals
and the cell surface (Pouran et al. 2017). Sph2 attached most onto hydrophobic,
electrostatically neutral polystyrene compared to hydrophilic and positively charged
hematite surface after 96 h of incubation (pH 6.5), please see the appendix for more
information and details of the experimental conditions.
Sphingomonas spp., Sph2 is a Gram negative bacterial species, which was
isolated from groundwater at a phenol-contaminated site in the West Midlands
(England) (Geoghegan et al. 2008; Andrews et al. 2009). In this research, we further
characterize its cell surface properties and try to elucidate the underlying reasons for
its attachment anomalies on the previously studied metal oxide surfaces (Pouran
et al. 2014, 2017).
Bacterial cells are expected to have relatively low point of zero charge (PZC), a
specific pH value at which the surface charge is neutral, and therefore have negative
surface charge in the pH range of natural environments (Ojeda et al. 2008; Pouran
et al. 2014, 2017; Andrews et al. 2010). Nevertheless, the dynamic nature of the
bacterial species allow them to adapt with different environmental conditions and
capable them of changing their surface chemistry (Claessens et al. 2004, 2006).
Presence of different biopolymers and nonuniform surface charge distribution means
that the bacterial surface charge is a very specific characteristic that depends on the
physiological and environmental conditions (Fein et al. 2005; Hong and Brown
2008). For example, we know that the ionic strength influences surface potential and
affects the electrokinetic and surface properties of the bacterial cells (Chen and
Walker 2007).
Here we aim to identify Sphingomonas spp., Sph2 cell wall functional groups for
the first time, determine its surface electrostatic nature, and explain its observed
attachment anomalies (tendency to form biofilm on the electrostatically neutral and
hydrophobic polystyrene compared to the positively charged hydrophilic metal oxide
surfaces) that we have seen in the previous studies (Pouran et al. 2014, 2017). For
these purposes we used Infrared spectroscopy, zeta potential measurements, potenti-
ometric titrations, and modelling techniques. In addition, the effects of different ionic
strengths on biofilm formation of Sph2 on the hematite surface were studied.
Experimental Section and Sphingomonas spp., Sph2 Case Study
In this section, we describe some of the most common techniques used to study the
cell surface of bacterial strains. We provide details of the performed experiments for
understanding Sphingomonas spp., Sph2 cell wall properties. The rest of this chapter
is focused on this bacterial strain as a case study. The chemicals used in this research
were certified ACS reagents, chemicals that meet or exceed the latest ACS specifi-
cations. Ultra-high quality water (UHQ, conductivity 18.2 MH/cm at 25 C) was
used throughout the experiments. By no means the methods mentioned in this
chapter are exhaustive. They are some of the most frequently used and basic tests
that scientists perform to analyze the bacterial cell surface properties. A range of
other techniques like Atomic Force Microscopy and Scanning Electron Microscopy
are available that could help to elucidate more features of these microorganisms like
their surface biopolymers.
Sph2 Growth Condition, and Preparation for Infrared Spectroscopy

of Its Cell Surface
Sph2 was grown in AB10 medium (a defined mineral medium with known exact
chemical composition) (Tolker-Nielsen et al. 2000) for 96 h, please see the appendix
for more information and details of the experimental conditions (Table 4). Immedi-
ately after the incubation, the bacterial cells were harvested by centrifugation and
washed in 10 ml of sterile 0.9% NaCl solution. To analyze Sph2 cell surface by
infrared spectroscopy, the harvested cells were re-suspended in 0.1 M NaCl and the
suspension pH was adjusted to 4, 6.5, and 9.0. These three pH values were
chosen to assay cell functional group changes in acidic, close to neutral (and the pH
of the pervious experiments (Pouran et al. 2009, 2014, 2017; Geoghegan et al.
2008)), and alkaline environments. To adjust the pH values to acidic and alkaline,
pH buffers were added to suspension of Sph2 cells in 0.1 M NaCl. For pH 6.5
instead of a pH buffer AB10 medium, which maintains the pH at this level, was added.
After 6 h, Sph2 cells were re-harvested from the pH adjusted samples (pH values of
the suspensions were also measured at the end of the exposures). The harvested Sph2
cells were mounted on the ATR-FTIR, attenuated total reflection-Fourier transform
infrared, to record their spectra at room temperature. Prior to scanning the samples,
as the harvested cells were still wet, the excess water was dried using pressurized
nitrogen gas. The measurements were performed using an ATR-FTIR system com-
prising of a Germanium crystal (Ge) attached to a Perkin Elmer Spectrum One Fourier
Transformation Infrared Spectrophotometer. For all samples, 200 infrared scans with
the resolution of 4 cm1 wavenumber were collected.
Potentiometric Titration of Sph2
Potentiometric titration experiments were performed using an automated potenti-

ometric titrator (Metrohm, 718 STAT, Titrino). The titration vessel consisted of a
Pyrex cell of 100 ml capacity with a rubber lid equipped with holes for electrode,
micro burette, thermometer, and N2 flushing plastic tube. Concentrations of 6.0 g/l
of freeze-dried Sph2 were titrated in three different concentrations of background
electrolytes (0.01, 0.1, and 0.3 M NaCl). Throughout the titrations, acid and base
were added by computer-controlled microburette with a dispensing volume of
0.01 ml. The titrator was adjusted to add successive acid or base when the absolute
value of the potential drift was equal or less than 5 mV/min. The cell suspensions
were purged by N2 gas for approximately 2 h before titration and the titration was
performed under N2 atmosphere. In these experiments, continuous stirring

was provided by magnetic stirrer and the suspension temperature was kept at
25 C during the titration period. A similar titration procedure was followed for
the blank solution. The collected titration data for the cell suspensions were
plotted in terms of moles of deprotonated sites per mass of bacteria and was
calculated by spread sheet (Fein et al. 2005). During this process, the surface
charge of Sph2 in the aqueous media was calculated using the following equations
(Eq. 1) (Ojeda et al. 2008; Fein et al. 2005; Stumm and Morgan 1996; Mustafa
et al. 2004).
Equation 1. Calculation of Sph2 consumed/released protons during adding acid

and/or base in an aqueous medium
ðCa Cb þ ½OH ½H þ Þ
δ0 ¼ (1)
m
In this equation, δ0 is molar equivalents of surface charge (mmol/g), Ca, and Cb
are concentrations (mol/l) of added acid and base to the cell suspension, respectively,
m is mass of the freeze-dried bacterial cell in suspension (g/l), and [H+] and [OH]
are molar concentrations of H+ and OH determined from measured solution pH. In
this research, the potentiometric titration curves of the bacterial strain were plotted as
a function of consumed proton concentrations versus suspension pH. PZC was
obtained as the common intersection point of titration curves for three different
concentrations of background electrolytes (0.01, 0.1, and 0.3 M NaCl).
Modelling Surface Protonation of Sph2 Based on the Titration Data
To calculate protonation constants from the titration data, ProtoFit 2.1 (a computer
program for analyzing potentiometric titration) was used to optimize the data.
ProtoFit has been used before to optimize surface protonation models from acid-
base titration data and to characterize the chemistry of bacterial cell walls (Ojeda
et al. 2008; Turner and Fein 2006; ProtoFit n.d.; Yue et al. 2015; Zhao et al. 2015).
To model the acidity constants, based on the experimental data, nonelectrostatic
and constant capacitance models [NEM and CCM] were used. In a non-
electrostatic model (NEM), electrostatic interactions are assumed to be negligible,
in other words no electrostatic effects affect adsorption, while the constant capac-
itance model (CCM) assumes that the charge distribution on the bacterial surface
is homogenous. These two models have been used before to model surface proton-
ation of different bacterial species (Ojeda et al. 2008; Turner and Fein 2006).
These calculations consider a functional group acidic when it releases a proton to
form a negatively charged surface species. A functional group is basic when it
adsorbs a proton to form a positively charged surface species as seen in Eqs. 2 and
3 (Ojeda et al. 2008; Dittrich and Sibler 2005).
Equation 2. Stoichiometric reaction for an acidic surface functional group

(>S = Surface)
> SOH $> SO þ H þ (2)
Equation 3. Stoichiometric reaction for a basic surface functional group

(>S = Surface)
> SOH þ
2 $> SOH þ H
þ
(3)
Zeta Potential Measurements
Zeta potential is defined as the electrical potential difference at the shear plane or
the interface between the bulk aqueous medium and static fluid layer attached to a
bacterial cell (Martinez et al. 2008), please see the appendix for more information
and details of the experimental conditions (Fig. 9). Sph2 zeta potential was
obtained in 1 mM KCl solution, adjusted to different pH values. A zeta potential
analyzer (Zeta Plus, Brookhaven Instruments, Huntsville, NY) was used for this
purpose. Zeta Plus is operating based on light scattering (laser beam) to determine
electrophoretic mobility of charged colloidal suspensions; in these studies, the
mean value of 10 readings was reported. In the previous publications (Pouran
et al. 2014, 2017; Geoghegan et al. 2008), Sph2 attachments on the mineral
surfaces were studied when the cells were grown and incubated in AB10 growth
medium, which has a high ionic strength, please see the appendix. To compare the
zeta potential obtained in 1 mM KCl solution with an ionic strength compatible to
the experimental conditions, Sph2 zeta potential in AB10 medium (ionic
strength = 196.08 mM) was measured. As seen in the appendix, NaCl has the
highest concentration in this defined growth medium. In fact, NaCl high concen-
tration in AB10 contributes to more than 91% of this medium ionic strength
(179 mM of 196.08 mM). Increasing ionic strength reduces the length of the
diffusive double layer formed at the surface of a charged colloidal particle (including
bacterial cells) and hampers the electrostatic interactions with other charged surfaces
(Pouran et al. 2014; Chen and Walker 2007). To better understand how changes in the
growth medium ionic strength affects Sph2 surface potential, the zeta potential was
also measured in AB10 media with altered ionic strengths. As mentioned earlier, in
AB10 more than 91% of the ionic strength is because of the sodium chloride
concentration. To reduce the original ionic strength from 196.08 mM to new levels,
NaCl initial concentration in AB10 was reduced to form two lower ionic strengths:
98.80 mM and 19.06 mM, and then Sph2 surface potential in these altered media were
measured. For more details please see the appendix.
Sph2 Biofilm Formation on Hematite
As shown in the previous studies (Pouran et al. 2009, 2014, 2017; Andrews et al.
2010; Geoghegan et al. 2008), this hydrophilic bacterial strain with expected negative
surface charge (in pH of the experiment, 6.5) shows negligible attachment on the
positively charged hydrophilic iron oxides surfaces after 96 h incubation in AB10
medium. To better understand how electrostatic interactions affect Sph2 attached
growth on the metal oxide mineral surfaces, hematite was chosen as the model metal
oxide mineral. The hematite used in this experiment has PZC 7.5, which makes it
positive in the experimental condition (pH 6.5) (Pouran et al. 2014, 2017). After
96 h incubation in AB10 growth medium with original and altered ionic strengths
(as explained in the previous section), 98.80 mM and 19.06 mM, the biofilm formed
by Sph2 on the hematite surface was evaluated through direct imaging, please see the
appendix for more information and details of the experimental conditions. The
experimental protocols including preparing the samples, staining the bacterial cells
for the direct imaging, and the direct imaging procedure have been explained in
details in the previous publications (Pouran et al. 2014, 2017).
Results and Discussions
Infrared Spectroscopy of Sph2 Cell Wall
Figure 1 shows the infrared spectra of Sph2 cells at three different pH values: 4, 6.5, and
9. As seen the observed spectra are compatible with the expected bacterial cell wall
characteristics and consistent with the most common and universal functional groups of
the bacterial surface: hydroxyl, carboxyl, phosphoryl, and amine groups (Claessens
et al. 2004, 2006; Ojeda et al. 2008; Turner and Fein 2006; Dittrich and Sibler 2005;
Dittrich and Luttge 2008; Fein 2006; Jiang et al. 2004; Vijayaraghavan and Yun 2008).
Changing the pH value from acidic to basic does not lead to unexpected changes in
Sph2 spectra. Deprotonation of the carboxylic group at higher pH values, present at
1720–1740 cm1, leads to lower intensity of this peak. These changes can be noticed
when it is compared with the peak at 1542 cm1. The contribution of C═O of esters to
this peak ( 1720–1740 cm1) prevents its complete disappearance due to
deprotonation of the carboxylic group (Ojeda et al. 2008; Dittrich and Sibler 2005;
Dittrich and Luttge 2008; Pouran et al. 2013). The suggested band assignments of Sph2
infrared spectra, based on the previous publications (Ojeda et al. 2008; Dittrich and
Sibler 2005; Dittrich and Luttge 2008; Jiang et al. 2004; Pouran et al. 2013; Yee et al.
2004), studying bacterial species cell surface functional groups, are shown in Table 1.
Sph2 Surface Potential in Different Ionic Strengths
Figure 2a demonstrates Sph2 surface potential values when suspended in 1 mM

solution of KCl. This figure clearly shows that this bacterial strain has negative
Fig. 1 The infrared spectra of Sph2 strain. After 96 h incubation in AB10 medium, bacterial cells
were washed and re-suspended in 0.1 M NaCl with different adjusted pH values
surface potential at approximately neutral pH values, which is consistent with the

expected, relatively low, point of zero charge of bacterial cells (Pouran et al. 2017;
Geoghegan et al. 2008; Claessens et al. 2004, 2006; Leone et al. 2007). Figure 2b
shows the dramatic impact of the solution ionic strength (IS) on Sph2 zeta potential.
Increasing the solution ionic strength from 1 mM KCl to approximately 200 mM
AB10 led to nearly 20 mV difference in the measured zeta potential of Sph2 cell
suspensions in the above-mentioned media. As seen the cell surface charge was close
to zero in AB10 medium (denoted IS1 in this figure). In Fig. 2a the most significant
change in the surface potential can be seen, when the solution ionic strength was
reduced from 98.08 mM (IS2) to 19.06 mM (IS3). This agrees with the previously
published studies that suggest in the ionic strengths above 100 mM role of the
Table 1 Absorption bands of the Sphingomonas spp., Sph2 functional groups

Wavenumber
(cm 1) Functional group assignment
~1740–1725 Stretching C═O of ester functional groups primarily from membrane lipids
and fatty acids, stretching C═O of carboxylic acids
~1645 Stretching C═O of amides associated with proteins
~1540 Bending of N─H and C─N stretching in amides, asymmetric stretching
C═O of carboxylate
~1458 Bending CH2/CH3 of proteins
~1402 Bending CH2/CH3 of proteins and stretching C─O of carboxylic groups
~1385 Stretching COO; bending CH2/CH3
~1315 Vibration of CH and CH2
~1255 Bending C─O of COOH, P═O stretching of phosphoryl groups
~900–1200 PO2 and P(OH)2 stretching in phosphates, C─C, C─O─C and C─OH
vibrations for polysaccharides
~1089 P═O stretching of phophorylated proteins, phosphate storage products, or
phophodiester
~976 Vibration of phosphoryl group
electrostatic interactions between the bacterial cells and their ambient environments
is weakened because of the hampered diffusive double layer (Pouran et al. 2014;
Chen and Walker 2007).
Sph2 Potentiometric Titration and the Data Optimization Using

ProtoFit
The potentiometric titration results show that Sph2 has PZC of approximately 4.3.
As Fig. 3 shows, the titration curves at different ionic strengths exhibit a common
intersection point approximately at pH 4.3. This value is compatible with the
obtained zeta potential for Sph2 through the direct zeta potential measurements
(Fig. 2a). In the data optimization process, the constant capacitance model (CCM),
which is based on the concept of homogenous charge distribution on the bacterial
surface (Ojeda et al. 2008; Turner and Fein 2006; Boily et al. 2001; Boily and Felmy
2008; Leone et al. 2007), was not able to provide a good fit to the potentiometric
titration data compared to the non-electrostatic model (NEM).
ProtoFit can be used to optimize surface protonation models with up to four
discrete surface sites (deprotonation constants) (Turner and Fein 2006). For Sph2
potentiometric data optimization based on NEM, two options were chosen; NEM
with three and four surface sites. Table 2, summarizes results of the data optimization
by ProtoFit. As seen in this table, both three- and four-site models show good fits,
but four-site model has a smaller weighted sum of squares value, SS*, which is an
indication of better fit. As these calculations indicate the ProtoFit calculated PZC
based on the four-site non-electrostatic model is compatible with the intersection
point of the titration curves (Fig. 3). Figures 4 and 5 respectively demonstrate
pH
a 0
3 4 5 6 7 8 9
–5
Zeta Potential (mV)
–10
–15
–20
–25
–30
Changes in surface potential as a result

b
of changing ionic strength
0.00
IS1 (196.08 mM) IS2 (98.08 mM) IS3 (19.06 mM) 1 mM KCI
Surface potential (mV)
–5.00
–10.00
–15.00
–20.00
–25.00
Fig. 2 (a) Zeta potential of Sph2 strain suspended in 1 mM of KCl at different pH values.
(b) Variations of the zeta potential of Sph2 strain in AB10 medium at different ionic strengths
calculated surface charge of Sph2 versus pH and compare fitting of the optimized
data to the raw potentiometric titration values based on the four-site (four
deprotonation constants) non-electrostatic model (NEM). As these figures suggest
the estimated values are compatible with the raw titration data.
Table 3 lists calculated acidity constants for Sphingomonas spp., Sph2. As
seen it also shows examples of using NEM to calculate the acidity constants
for other bacterial species (Fein et al. 2005; Ojeda et al. 2008; Yee et al. 2004). In
this table, C indicates the concentration in 104 mole/g. In Gram-negative bac-
terial cells, the outermost layer consists of lipopolysaccharide. Although, the
Fig. 3 Potentiometric titration data for 6 g/l (dry weight) of Sphingomonas spp., Sph2 in three
different background electrolytes
Table 2 Deprotonation constants and point of zero charge (PZC) as calculated by ProtoFit
using NEM
No of sites pK1 pK2 pK3 pK4 pZC SS*
3 3.9 0.2 5.9 0.4 9.4 0.2 – 4.37 4.18*102
4 4.1 0.3 5.9 0.2 8.9 0.0 10.2 0.1 4.55 2.90*102
SS*value is weighted sum of squares and reflects the goodness of fit
Gram-positive bacteria do not have this layer, they show similar surface charge
pattern and PZC values, which may suggest that lipopolysaccharide is not a
major contributor to the bacterial cell wall charge (Pouran et al. 2017; Claessens
et al. 2006; Ojeda et al. 2008). Concentrations of the surface sites for Sph2 are
within the range of reported surface functional groups’ concentrations. Total
concentrations as low as 0.78 104 mol/g and as high as 16.6 104 mol/g
have been reported in the previous studies (Ojeda et al. 2008; Dittrich and Sibler
2005). Although, the Sphingomonas species are Gram-negative but are unique
among other bacterial species in this group. Instead of the lipopolysaccharide
(LPS) layer, the Sphingomonaceae family have glycosphingolipids (GSL)
Fig. 4 Calculated surface charge by Protofit modeling tool for Sph2. The four-site NEM model is
applied
(Pouran et al. 2014, 2017). Glyscosphingolipids are a subgroup of glycolipids

(lipids that are linked to a carbohydrate chain) and contain an sphingosine (amino
alcohol) moiety (Gutman et al. 2014; Kawahara et al. 2001; Varki et al. 2008).
For further information about glycosphingolipids, please see the appendix.
Calculated Sph2 pKa values for the four-site model are 3.9 0.3, 5.9 0.2,
8.9 0.0, and 10.2 0.1, respectively. These pKa values could be tentatively
assigned to carboxyl (2 pKa 6), phosphoryl (5.6 pKa 7.2), amine
(8.6 pKa 9), and hydroxyl (8 pKa 12) groups (Ojeda et al. 2008; Dittrich
and Sibler 2005; Jiang et al. 2004). For the four-site NEM: carboxyl, phosphoryl,
and hydroxyl groups were assumed to be acidic functional groups, while amine
considered to function as a basic group on the Sph2 cell surface. The definitions of
acid and basic functional groups in this research have been mentioned in the
previous sections (please see Eqs. 2 and 3). The proposed protonation/deprotonation
reactions of Sph2 cell wall functional groups are shown in the following equations
(Eqs. 4–7).
Equation 4. Deprotonation of the carboxyl group (acidic functional group).

>R- is the side chain
> R CO2 H $> R CO

2 þH
þ
(4)
Fig. 5 Fitting of four-site nonelectrostatic model (NEM) to raw titration data. The raw titration
graph corresponds to the second step of titration when NaOH is added to initially acid-added
suspension
Equation 5. Deprotonation of the phosphoryl group (acidic functional group).

> R PO3 H 2 $> R PO3 H þ H þ (5)
Equation 6. Deprotonation of the hydroxyl group (acidic functional group).

> R OH $> R O þ H þ (6)
Equation 7. Deprotonation of the amine group (basic functional group).

> R NH þ
3 $> R NH 2 þ H
þ
(7)
46
Table 3 Comparison of deprotonation constants and surface site concentrations between Sphingomonas spp., Sph2 and some of other strains from different
studies. NEM is used for all of these strains. Concentrations are shown in 104 mol/g
C
Species pK1 pK2 pK3 pK4 total C1 C2 C3 C4
Sphingomnas spp., Sph2 gram- 3.9 0.3 5.9 0.2 8.9 0.0 10.2 0.1 4.70 1.79 0.3 0.56 0.0 1.19 0.3 1.16 0.2
negative
Bacilus subtilis gram-positive 3.3 4.7 6.8 8.9 2.77 0.75 0.96 0.31 0.75
Calothorix sp. gram-negative 4.7 0.4 6.6 0.2 9.1 0.3 N/A 14.6 3.3 0.3 4.1 0.3 7.16 1.0 N/A
Aquabacterium commune gram- 3.5 0.8 5.7 0.9 9.1 1.6 N/A 14.2 4.6 1.5 1.9 0.6 7.3 3.1 N/A
negative
Characterizing the Cell Surface Properties of Hydrocarbon-Degrading. . .
1153
Sph2 Biofilm Formation on the Hematite Surface Under Different

Ionic Strengths
Sph2 zeta potential measurements in the solutions with different ionic strengths
(Fig. 2) underline the role of the growth medium’s ionic strength in the electrostatic
behavior of this bacterial species. In other words, changing the solution ionic
strength and consequently Sph2 surface potential should lead to a different attach-
ment behavior. Figure 6 shows biofilm formation of Sph2 on the hematite surface
after 96 h incubation in AB10 medium with the original and altered ionic strengths.
This figure also displays the quantified number of the attached cells. As can be seen,
when the ionic strength was reduced by a factor of ten, the number of the cells
attached to the hematite increased approximately tenfold. The difference in Sph2
surface potential under these two conditions is approximately 20 mV, which
reinforces the electrostatic attraction between positively charged hematite and a
negatively charged Sph2 surface. This figure indicates that the electrostatic interac-
tions between the hematite and Sph2 surface plays an important role in the number of
attached cells.
The electrostatic behavior of the bacterial surfaces is considerably more complex
than minerals. The presence of different types of biopolymers at the cell surface,
which can undergo conformational changes, can also influence the bacterial cell
adhesion to the mineral surfaces (Andrews et al. 2010; Geoghegan et al. 2008).
Changing the solution’s ionic strength induces such conformational changes to the
bacterial surface polyelectrolytes. Bacterial polyelectrolytic polymeric layers that
extend out the cell wall can function like anchors and aid the adhesion when the cell
approaches a surface (Hong and Brown 2008; Emerson et al. 2006). These cell
Fig. 6 Attachment of Sph2 to the hematite surface under different ionic strengths
(a: IS = 196.08 mM, b: IS = 98.08 mM, c: IS = 19.06 mM). Quantified number of cells attached
to hematite after 96 h of incubation under different ionic strength (IS) conditions
surface biopolymers show conformational changes due to changing the solution

chemistry, specifically ionic strength and pH (Chen and Walker 2007; Redman et al.
2004). The presence of protons (low pH values) and/or high ionic strengths can
change cell surface polymers from stretched to coiled forms as well as altering the
rigidity of these macromolecules (Geoghegan et al. 2008; Abu-Lail and Camesano
2003). In an opposite way, increasing pH and decreasing the ionic strength leads to
increasing ionization of the biopolymers and electrostatic interaction (repulsion)
between the side chains. These non-screened electrostatic interactions cause lack
of conformational stability of the surface polymers and random shape polymer
structures (Fedorov et al. 2009), please see the appendix for more information and
details of the experimental conditions.
In the case of hematite-Sph2 interface, increasing the ionic strength shortens the
distance, in which effective electrostatic attraction between these two surfaces
occurs. In addition, due to the expected relatively rigid and compressed coiled
conformation of Sph2 surface polymers in the high ionic strength conditions, these
biopolymers become less capable of interacting with the hematite surface within a
fixed distance from the surface. By reducing the ionic strength from approximately
200 mM to 20 mM, the cell surface polymers can be extended out and
have random stretched shapes, which in addition to the stronger electrostatic
attraction between the hematite and Sph2 likely aid Sph2 attachment to the
hematite surface.
Hydrogen bonding, although not as important as electrostatic interactions and
biopolymers conformational changes, may also contribute to the adhesion behavior
of Sph2 on the hematite surfaces. All sphingolipids have a hydrophobic backbone
due to ceramide. Ceramide can be defined as the lipid moiety of glycosphingolipids;
it consists of sphingosine (aminoalcohol with unsaturated hydrocarbon chain) and
fatty acid (Lackie 2007). They are distinguished by the presence of a planar system
including the amide to the hydroxyl groups disposed at the water/lipid interface.
Sphingolipids act as both donors and acceptors to form hydrogen bonds, and that is
because of the presence of amide, carboxyl, and hydroxyl groups (Prinetti et al.
2009a). In the pH of the experiment (pH 6.5), the hematite surface is positively
charged and protonated. This suggests that though the hydrogen bonds still may
form between Sph2 surface polymers and few deprotonated sites on the hematite, its
contribution to the biofilm formation is considerably less important than the elec-
trostatic interactions or conformational changes of the biopolymers in the lower
ionic strengths.
Conclusions
Surface properties of a Gram-negative bacterium Sphingomonas spp., Sph2 (isolated

from groundwater at a phenol-contaminated site) and effects of the growth medium
ionic strength on its adhesion to hematite were investigated. The ATR-FTIR
analysis showed that despite the unique cell wall chemistry of Sph2 (as a
member of Sphingomonaceae family and having glycosphingolipids instead of
lipopolysaccharide) among the Gram-negative strains, its cell wall infrared

spectra are compatible to other bacterial cells. Hydroxyl, carboxyl, phosphoryl,
and amide groups were detected in Sph2 infrared spectra. The
potentiometric titrations were performed between pH 3.5 to 10 in three different
background electrolytes. The titration data indicated that Sph2 point of zero
charge is 4.3. ProtoFit modeling showed that four-site non-electrostatic
model (NEM) provides a good fit to the raw titration data. The pKa values for
these four sites are 3.9 0.3, 5.9 0.2, 8.9 0.0, and 10.2 0.1, which could
be assigned to carboxyl, phosphate, amine, and hydroxyl groups, respectively.
Based on the four-site NEM, calculated PZC for Sph2 is 4.55, which agrees with
the titration data.
Measured zeta potential for Sph2 in 1 mM KCl was approximately 20 mV.
However, this value considerably changed in AB10 medium and moved
towards zero. Alterations of AB10 ionic strength (by changing NaCl con-
centrations in this defined mineral medium) from 20 mM to 100 mM
shifted Sph2 surface potential from 20 mV to 5 mV. This shift was
considerably less, 3 mV, when the ionic strength was increased from
100 mM to 200 mM. Changing the solution ionic strength and consequently
surface potential led to dramatic increase in the number of the attached cells to the
hematite surface. Electrostatic interactions, conformational changes of the cell
surface biopolymers, and to considerably less extent hydrogen bonding can all
contribute to the adhesion patterns of Sph2 to the metal oxides. Nevertheless,
distinguishing the degree of contribution of each of them requires further
investigation.
Cross-References

and Prioritizing the Cost-Effective, Eco-friendly, and Sustainable Biotechnologi-
cal Intervention
▶ Bacterial Cell-mineral Interface, Its Impacts on Biofilm Formation and
Bioremediation
▶ Bioremediation of Hormones from Waste Water
▶ Bioremediation of Mined Waste Land
▶ Biostimulation and Bioaugmentation: An alternative Strategy for Bioremediation
▶ Characterizing the Cell Surface Properties of Hydrocarbon-Degrading Bacterial
▶ Development of an Environmentally Sustainable Approach for Safe Disposal of
Arsenic-Rich Sludge

Appendix
Preparing the Hematite Surface for Cell Adhesion Studies (Synthesis,

Coating, and Characterization)
Hematite was prepared by heating an acidic solution of FeCl3. A STOE STADI P

X-ray powder diffractometer and a Perkin Elmer Spectrum Spotlight FTIR imaging
system for Fourier-transform infrared spectroscopy (FTIR) were used to analyze the
synthetized materials. For XRD analysis, copper K alfa was the radiation source; a
range of 10–70 degrees and a step size of 0.02 degrees were the test parameters. In
FTIR experiments, the spectrum resolution was 4 cm1, covering the range of
4000–400 cm1 wave numbers, and 150 scans were collected for each sample.
To determine the point of zero charge (PZC) of the synthetic metal oxide,
potentiometric titration was done. An automated potentiometric titrator (Metrohm,
718 STAT, Titrino) was used. During titrations, acid (HCl, 0.1 M) and base (NaOH,
0.1 M) were added by a computer-controlled microburette with a dispensing volume
of 0.01 ml. The titrator was adjusted to add successive acid or base when the absolute
value of the potential drift was equal to or less than 5 mV/min. The sample
suspensions were purged with N2 gas to remove carbon dioxide from the system
for approximately 2 h before titration, which was performed in an N2 atmosphere. In
these tests, a magnetic stirrer provided continuous stirring and the suspension
temperature was kept at 25 C during the titration period. Surface hydrophobic/
hydrophilic properties of the synthetic minerals were obtained by measuring the
water-drop contact angle in air. Contact angles were obtained using the sessile drop
method and a KRÜSS DSA 100 drop-shape analysis system. An aliquote of 3 μl of
UHQ water was added to the mineral surfaces at room temperature. The contact
angle between the surface and a tangent drawn on the drop surface, passing through
the triple point of atmosphere-liquid-solid, was measured. Iron oxides’ hydrophilic
nature stems from their surface hydroxyl groups. In general, surfaces with a water-
drop contact angle of less than 90 degrees are hydrophilic; nevertheless, for the
surfaces studied, the expected water-drop contact angles were considerably less.
The coating process involved the direct deposition of mineral particles from an
aqueous suspension by evaporation, which has been explained in detail in previous
publications (Pouran et al. 2014, 2017). After this step, the coated polystyrene
surfaces were assessed using optical microscopy (Zeiss, Axiovision), direct imaging,
and contact-angle measurements to determine their hydrophobicity (as described
above). The ATR-FTIR, attenuated total reflection-Fourier transform infrared, tech-
nique using a Specac Silver Gate Essential Single Reflection ATR System and XPS,
and X-ray photoelectron spectroscopy (KRATOS-Axis 165) were also used to

compare the chemical properties of altered surfaces with those of reference polysty-
rene and mineral surfaces (Pouran et al. 2014).
Bacterial Strains, Growth Conditions, and Sample Preparation
Six bacterial strains were isolated for bacterial-adhesion and attached-growth stud-
ies. Rhodococcus spp., RC92 and RC291, both Gram-positive, were isolated from
soil samples from a polluted gasworks site in northeast England. The bacteria
Pseudomonas spp. (Pse1 and Pse2) and Sphingomonas spp. (Sph1 and Sph2) were
isolated from groundwater at a phenol-contaminated site in the West Midlands
(England). The strains Pse1, Pse2, Sph1, and Sph2 are Gram-negative. They have
been classified using comparative 16S rRNA sequencing (Geoghegan et al. 2008).
All strains were maintained on a solid R2A medium (Oxoid).
The bacterial strains were grown in an AB10 medium, which is a defined medium
with known exact chemical composition. The carbon source was 2 mM of glucose,
and the incubation time was 96 h at 20 C on a shaker at 150 rpm. After incubation,
cells were harvested by centrifugation in an early stationary phase and washed in
10 ml of sterile 0.9% NaCl solution. Samples of washed and resuspended strains
(in 0.9% NaCl), with an optical density (OD) of 0.01 at λ = 600 nm, were
resuspended in the AB10 medium. The aim of this study was to perform experi-
ments, including bacterial cell growth and attachment, in a well-controlled
environment.
Biofilm Formation Studies
Six strains, four different surfaces, two carbon sources, and one experimental control
(AB10 medium with no carbon source) were analyzed in triplicate to assay biofilm
formation for a total of 216 samples. In these experiments, reference polystyrene
plates were prepacked and radiation-sterilized. The mineral-coated polystyrene
plates were sterilized by immersion in a 70% ethanol medium for 1 h prior to
incubation and dried under aseptic conditions in a laminar flow cabinet.
Noninvasive, in situ direct imaging using Syto9 stain (green fluorescent nucleic
acid stain, supplied by Invitrogen) was used as the primary technique to assay
biofilm. The reference polystyrene and metal-oxide coated polystyrene well-plates,
each with 12 wells and a nominal culture area of 3.82 cm2 for each well, were used
as substrata for biofilm formation studies. Samples of bacteria suspension were
prepared at an optical density (OD) of 0.01 at λ = 600 nm using AB10 medium,
pH 6.5. Then, 2 ml of prepared medium was added to each micro-well.
The 12 well-plates were incubated for 96 h at 20 C (Fig. 7); then, 200 μl of each
of the bacterial samples, from their planktonic phase, was transferred to a 96-micro
well-plate and the OD was measured at λ = 630 nm to determine planktonic phase
growth. To assess the planktonic phase of individual environmental isolates, the
Fig. 7 Schematic representation of incubating polystyrene and mineral-coated 12-well plates and
directly imaging the strains attached to the studied surfaces. (a) Depicts confined lateral movements
of the water-dipping objective due to the well’s sides. As seen, a circle of diameter 11 mm located at
the centre of each well’s base was imaged for the studied substrata. (b) Shows direct imaging of the
aluminium hydroxide-coated plates. (c) Illustrates the function of Z-height focusing, Z stacking,
used in evaluating biofilm formation. This method was used for dense biofilms to better assess the
numbers of cells attached to polystyrene and mineral surfaces
Fig. 8 Total number of bacterial cells attached to mineral-coated polystyrene and polystyrene
surfaces after 96 h of incubation in AB10 medium with a glucose carbon source
measured optical density (OD) at λ = 630 nm was calibrated against the number
of colony-forming units (CFU) for each strain. This calibration was used to
compare growth in the planktonic phase for each individual strain. The rest of the
planktonic phase was discarded and each well was gently washed three times by
adding 5 ml of 0.9% sterile NaCl solution that was slowly added to the well
wall and bottom intersection, using a pipette tip, to remove cells in the planktonic
phase and ensure that only bacterial cells which had attached to the surface were
present.
Each well of the reference polystyrene and coated plates was stained by adding
0.5 ml of Syto 9, which was diluted 500. The thickness of the added stain layer
that formed on the bottom of the well was approximately 1.25 mm (the surface
area of each well was 3.82 cm2). The stained wells were directly imaged in situ
using a 100 magnification Zeiss Achroplan water-dipping objective (Fig. 7).
For imaging, a Zeiss AxioVision epifluorescence microscope with automated
Z-height focusing (Z-stacking) was used for extended depth and field imaging.
With this technique, a series of images are acquired at different focus positions,
which allows imaging through a thick section or of a rough surface (Fig. 7).
Images were captured with an Axiocam black & white camera using a
450–490 nm narrow-band pass filter. For each sample, 15 images were captured
and then analyzed using AxioVision 4.6 and Image J software. From these digital
Fig. 9 Schematic representation of distribution of electric charges and position of zeta potential
around a negatively charged bacterial cell
images, direct cell counts were obtained and reported as cells/cm2 (since each
experiment was conducted in triplicate, each data point represents an average of
45 data points). The microscope water-dipping objective had restricted lateral
motion, due to the well’s sides, which confined the imaging area. Images to study
bacterial cell attachment on the substrate, at the bottom of each well, were taken
from a circular accessible surface with a diameter of 11 mm located at the center
of the wells. As mentioned earlier, microscope Z-stacking provided the option of
acquiring images at different focus positions. This technique was used to deter-
mine biofilm depth when the cells had formed dense biofilms (Figs. 8 and 9)
Glycosphingolipids
(Table 4).
These chemical structures are amphiphilic molecules and generally possess simi-
larities with physicochemical and functional properties of the LPS (Gutman
et al. 2014; Kawahara et al. 2001). Glycosphingolipids have a versatile chemical
Table 4 AB10 medium and its ionic strength

Element 1 Element 2
mM mM Ionic
No Chemical Concentration Valence Concentration Valence Strength
1 (NH4)2SO4 3.02E + 00 1 1.51E + 00 2 4.53E + 00
2 Na2HPO4 6.74E + 00 1 3.37E + 00 2 1.01E + 01
3 KH2PO4 2.20E + 00 1 2.20E + 00 1 2.20E + 00
4 NaCl 1.79E + 02 1 1.79E + 02 1 1.79E + 02
5 CaCl2 1.00E-02 2 2.00E-02 1 3.00E-02
6 MgCl2 1.00E-01 2 2.00E-02 1 2.10E-01
7 C6H12O6- 2.00E-01 0 0.00E + 00 0 0.00E + 00
glucose
8 FeCl3 1.00E-03 3 3.00E-03 1 6.00E-03
9 CaSO4 1.47E-06 2 1.47E-06 2 5.88E-06
10 FeSO4.7H2O 7.20E-07 2 7.20E-07 2 2.88E-06
11 MnSO4.H2O 1.18E-07 2 1.18E-07 2 4.73E-07
12 CuSO4 1.25E-07 2 1.25E-07 2 5.02E-07
13 ZnSo4.7H2O 6.96E-08 2 6.96E-08 2 2.78E-07
14 CoSO4.7H2O 3.56E-08 2 3.56E-08 2 1.42E-07
15 NaMoO4. 4.98E-08 1 4.98E-08 1 4.98E-08
H2O
16 H3BO3 8.09E-08 1 8.09E-08 1 8.09E-08
Solution ionic strength in mM = 1.96E + 02
AB10 original medium (IS1 = 196.08 mM, [NaCl] = 179.00), AB10-IS2 (IS2 = 98.08 mM,
[NaCl] = 81.00), AB10-IS3 (IS3 = 19.06 mM, [NaCl] = 2.52)
structure and can be found in the cell membranes of different organisms. Figure 10
shows the chemical structure of a glycosphingolipid; Gangiloside (GT1b) (Varki
et al. 2008). Sph2 are unique among all Gram-negative bacteria as they have
glycosphingolipid (GSL) instead of lipopolysaccharide (LPS) layer.
Glycosphingolipid has a functional role in cell-cell recognition and signalling
(Hakomori and Igarashi 1995); GSL molecular structure exhibits more than 200 var-
iations in carbohydrate structure, which can be combined with at least ten common
molecular species of ceramide (a composition of sphingosine and a fatty acid). This
combination can create over 2000 possibilities of GSLs molecular species
(Hakomori and Igarashi 1995). The presence of GSLs also can influence membrane
proteins architecture as several classes of membrane associated proteins display
a strong preference for the association of lipid-rich membrane domains (Prinetti
et al. 2009).
Some research shows that by changing KCl concentration from 0 to 100 mM,
Pseudomonas putida KT2442 cell wall biopolymer length changes from 440 nm to
160 nm (pH = 8) (Abu-Lail and Camesano 2003). Biopolymers can undergo a salt-
induced conformational change from a soft, random structure in low ionic strength to
Fig. 10 Chemical structure of a glycosphingolipid molecule, Gangiloside (GT1b)
Fig. 11 Schematic representation of conformational changes of biopolymers due to changes in

ionic strength. Low IS favors attachment, while high IS hinders it
a rigid structure in a highly ionic medium (Fig. 11). The effects of sodium chloride
concentrations on Poly-L-glutamate (PGA) as a multifunctional biopolymer has
been mentioned in the previous studies as a small amount of NaCl switches the
preferred conformation of this polymer. Adding a concentration of 0.3 M NaCl to
DI-water is sufficient to keep the dominant conformation of Poly-L-glutamate a
complex α-helix rather than an extended structure, on a nanosecond time scale
(Fedorov et al. 2009).
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Preparation, Characterization, and Heavy
Metal Ion Adsorption Property of APTES- 47
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with Original Clay
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Contents
Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1168
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1168
Kaolin and Modified Kaolin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1169
Kaolin in the Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1169
Structural Features . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1171
The Main Important Characteristics of Kaolin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1172
Functionalization of Kaolin with 3-Aminopropyltriethoxysilane (APTES) . . . . . . . . . . . . . . . 1180
Heavy Metals Removal by Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1183
Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1185
Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1185
Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1186
Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1187
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1189
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1189
Abstract
Surface modification of clay minerals has become increasingly important for
improving the practical applications of clays such as fillers and adsorbents. In
this study, we developed an effective adsorbent for retention of Co(II), Ni(II),
Cu(II), and Zn (II) by modifying kaolin clay with an amino-terminated
organosilicon (3-aminopropyltriethoxysilane, APTES). The lamellar filler (orig-
inal clay) used is the kaolin (K08) from Bechar–Algeria region. Characterization
of modified clay material and original clay was carried out by different methods
XRD, FTIR, TGA, and SEM to establish the link between syntheses, structures,
and properties. The adsorption of heavy metal ions onto APTES-modified kaolin
showed greater efficiency than original kaolin. These results indicate that the
B. Meroufel · M. A. Zenasni (*)

Faculty of Technology, University Abou Bekr Belkaïd of Tlemcen, Tlemcen, Algeria

https://doi.org/10.1007/978-3-319-73645-7_132
1168 B. Meroufel and M. A. Zenasni
APTES-modified kaolin may be used as very effective adsorbent for removal of

heavy metals from aqueous media.
Keywords
Clay · Kaolin · Modified kaolin · Heavy metal · Adsorption
Abbreviations
APTES 3-Aminopropyltriethoxysilane
K08 Kaolin of Bechar
KS Modified kaolin by 3-aminopropyltriethoxysilane
Definitions
Clay Although broadly distributed and well known, clays are difficult to
define precisely. The term is applied to finely grained natural
materials which are plastic when wet and hard and brittle
when dried, especially after firing. They are usually complex
mixtures of various minerals, with the main component being a
platy aluminosilicate.
Kaolin A clay where the principal clay mineral is kaolinite, but significant
amounts of other minerals can be present.
Heavy Metal Cobalt, nickel, copper, and zinc are some of the metals (called
“heavy” because of their high relative atomic mass) which persist
in nature and can cause damage or death in animals, humans, and
plants even at very low concentrations (1 or 2 micrograms in some
cases). Used in industrial processes, they are carried by air and water
when discharged in the environment. Since heavy metals have a
propensity to accumulate in selective body organs (such as the
brain and liver), their prescribed average safety levels in food or
water are often misleadingly high.
Introduction
Over the years, the percolation of heavy metals into the water bodies and ecosystem
remains as one of the most elusive and pervasive environmental threat to the global
occupants. Heavy metal ions are classified as priority pollutants based on their
toxicity and mobility in natural water streams. Nevertheless, the heavy metal ions
are stable and persistent to environment changes since they cannot either be
degraded or destroyed (Demirbas 2008). The increment of industrialization has
47 Preparation, Characterization, and Heavy Metal Ion Adsorption. . . 1169
aggravated the situation due to the mass loading of highly concentrated metal ion
containment effluent into the waterways.
The feasibility and reliability of lignocellulosic biomass, natural clay min-
erals, and biological-based materials used as low-cost adsorbent have been
evaluated by many researchers. These materials include sugarcane bagasse, risk
husk, tea leaves, bamboo dust, maize cob, tree sawdust (Mohamad Ibrahim et al.
2013), zeolite (Mohamad Ibrahim et al. 2010; Castaldi et al. 2008), bentonite
(Karapinar and Donat 2009), montmorillonite (Ijagbemi et al. 2009), kaolin
(Meroufel et al. 2013), Cephalosporium aphidicola (Tunali et al. 2006), Pinus
sylvestris Ucun et al. 2003), Saccharomyces cerevisiae (Huang et al. 1990), and
so forth.
Kaolin has received considerable recognition as an adsorbent because of its
high adsorption capacity. It is generally referred to as clay that is mainly com-
posed of kaolinite and a lower amount of minerals such as quartz and mica. It is
the most abundant mineral in soils and sediments and interacts with other soil
elements to contribute to the mechanical stability of the soil column (Chen et al.
2000). The adsorption properties of kaolinite are likely determined by its surface
structure and the edges (Schoonheydt and Johnston 2006). The edges possess a
variable charge that can be correlated to the reaction between ionizable surface
groups along the edges and the clay mineral surface and the ions present in
aqueous solution.
The modification process for this clay is based on the strategy commonly used for
kaolin functionalization. It consists of a direct condensation reaction between
3-aminopropyltriethoxysilane (APTES) and the hydroxyl groups of the clay minerals.
In this work, we modified kaolin with organosilicon (3-aminopropyltriethoxysilane,
APTES) to investigate kinetics and the mechanism of adsorption of Co(II), Ni(II),
Cu(II), and Zn (II) onto modified kaolin (KS). Langmuir and Freundlich equations
were used to determine the isotherm which gives the best correlation with experimental
data. Pseudo-second-order model was used to evaluate the adsorption kinetics for both
adsorbents.
Kaolin and Modified Kaolin
Kaolin in the Environment
Clays are hydrous aluminosilicates broadly defined as those minerals that make up
the colloid fraction (< 2 μm) of soils, sediments, rocks, and water (Pinnavaia 1983)
and may be composed of mixtures of fine-grained clay minerals and clay-sized
crystals of other minerals such as quartz, carbonate, and metal oxides. Usually the
term clay is used for materials that become plastic when mixed with a small amount
of water. Clays play an important role in the environment by acting as a natural
scavenger of pollutants by taking up cations and anions either through ion exchange
or adsorption or both. Thus, clays invariably contain exchangeable cations and

anions held to the surface. The prominent cations and anions found on clay surface
are Ca2+, Mg2+, H+, K+, NH4+, and Na+ and SO42, Cl, PO43, and NO3. These
ions can be exchanged with other ions relatively easily without affecting the clay
mineral structure.
Large specific surface area, chemical and mechanical stability, layered
structure, high cation exchange capacity (CEC), etc. have made the clays
excellent adsorbent materials. Both Brönsted and Lewis types of acidity in clays
(Tanabe 1981) have boosted the adsorption capacity of clay minerals to a great
extent. The Brönsted acidity arises from H+ ions on the surface, formed by
dissociation of water molecules of hydrated exchangeable metal cations on the
surface:
nþ ðn1Þþ
M ðH 2 O Þx ! MðOHÞðH2 OÞx1 þ Hþ (1)
The Brönsted acidity may also arise if there is a net negative charge on the surface
due to the substitution of Si4+ by Al3+ in some of the tetrahedral positions and the
resultant charge is balanced by H3O+ cations. The Lewis acidity arises from exposed
trivalent cations, mostly Al3+ at the edges, or Al3+ arising from rupture of Si–O–Al
bonds, or through dehydroxylation of some Brönsted acid sites. The edges and the
faces of clay particles can adsorb anions, cations, and nonionic and polar contam-
inants from natural water. The contaminants accumulate on clay surface leading to
their immobilization through the processes of ion exchange, coordination, or
ion–dipole interactions. Sometimes the pollutants can be held through H-bonding,
van der Waals interactions, or hydrophobic bonding arising from either strong or
weak interactions. The strength of the interactions is determined by various struc-
tural and other features of the clay mineral. van Olphen (van Olphen 1977) has cited
several types of active sites in clays, viz.:
(i) Brönsted acid or proton donor sites, created by interactions of adsorbed or
interlayer water molecules
(ii) Lewis acid or electron acceptor sites occurring due to dehydroxylation
(iii) Oxidizing sites, due to the presence of some cations (e.g., Fe3+) in octahedral
positions or due to adsorbed oxygen on surfaces
(iv) Reducing sites produced due to the presence of some cations (e.g., Fe2+)
(v) Surface hydroxyl groups, mostly found in the edges, bound to Si, Al, or other
octahedral cations
The present study determined the mineralogy and thermal properties of
kaolin from Tabelbala (Algeria). For many centuries kaolinic clays have been
exploited in the Tabelbala (Algeria) as a cement or waterproof cover on the
roofs. They are associated with lower Paleozoic sandstones. In the context of the
valorization of Algeria’s natural resources, a clay collected at Tabelbala in
the Bechar region (southwestern Algeria) and its clay fraction (particles with a
diameter of less than 2 μm) have undergone a series of mineralogical, chemical, and
physicochemical analyses.
Tabelbala is a department of the province of Bechar, located about 145 km

southwest of Béni Abbès and 400 km south of Bechar (Fig. 1). Tabelbala consists
of several small villages, the largest of which are Sidi Zekri to the east and Ksar
Cheria and Makhlouf to the west. There is a deposit of kaolin in Makhlouf, a
prodigious wealth (Fig. 2).
Structural Features
The structural features of the clays are well established. Kaolinite has a 1:1 layer
structure, first suggested by Pauling (Pauling 1930), with the basic unit consisting of
Fig. 1 Location of Tabelbala in far southwest of Bechar (Algeria). Location of Makhlouf quarry
Fig. 2 Deposit of kaolin in Makhlouf–Tabelbala–Bechar

Fig. 3 Structure of kaolinite
OH
OH OH OH
OH OH
=O = Shared O = Si = Al
a tetrahedral sheet of SiO4 and an octahedral sheet with Al+3 as the octahedral cation.
Both the sheets combine to form a common layer such that the tips of the silica
tetrahedra point toward the octahedral layer. The tetrahedral layer is inverted over the
octahedral layer with the apical “O” atoms being shared by the two layers (Fig. 3). In
the layer common to the octahedral and tetrahedral sheets, two-thirds of the O-atoms
are shared between Si and Al atoms. The remaining one-third of the sites in this layer
consists of hydroxyl groups coordinated to the octahedral Al atoms alone.
Two-thirds of the possible positions in the octahedral sheet are filled with Al, and
the remaining one-third of the sites are vacant. The Al atoms are placed in such a
manner that any two Al atoms are separated by two hydroxyl groups, one above and
one below, making a hexagonal distribution in a single plane in the center of the
octahedral sheet. The hydroxyl groups are placed directly against the centers of
oxygen hexagons of the basal plane of the tetrahedral layer (Theng 1979).
Kaolinite, (Si4)IV(Al4)VIO10(OH)8, has the theoretical composition of SiO2 46.54%,
Al2O3 39.50%, and H2O 13.96% expressed in terms of the oxides. The formula indicates
that there is no substitution of Si4+ with Al3+ in the tetrahedral layer and no substitution
of Al3+ with other ions (e.g., Mg2+, Zn2+, Fe2+, Ca2+, Na+, or K+) in the octahedral layer.
Thus, the net layer charge of kaolinite is [4 (+4)] + [4 (+3)] + [10 (2)] + [8 (1)] = 0,
but in nature, kaolinite has a small net negative change arising from broken edges on the
clay crystals. This negative charge, although small, is responsible for the surface not
being completely inert. Some workers have also reported substitution of octahedral Al3+
with Fe2+ and/or Ti4+ in kaolinite (Deer et al. 1985).
The Main Important Characteristics of Kaolin
The granulometric analysis indicates that the particles with a diameter of <2 μm
(clay phase) represent 40.15% of the total rock.
The cation exchange capacity (CEC) of the clay is 15 meq/100 g, and its specific
surface area (SSA) is 120 m2 g1.
X-Ray Diffraction
The mineralogy was determined by X-ray powder diffraction (XRD). X-ray exper-
iments were conducted using a Shimadzu XRD-6000. Intensity vs. scattering angle
(2Ɵ) was recorded at room temperature in the range 5–758 (2Ɵ), with step size of
0.028 and scanning rate of 28/min. X-ray experiments were conducted in samples
before and after the thermal treatment and also after the chemical treatments to
evaluate the effects of the treatments on the kaolinite structure.
X-ray diffraction (XRD) of the total crude rock shows that the essential clay
minerals of this clay are 47% kaolinite, 25% quartz, 17% illite, and the remainder
(dickite, alumite, and aluminum oxide alumina) 11%.
The X-ray diffraction spectrograph of the kaolin clay is shown in Fig. 4. Kaolin
shows three intense diffraction peaks at 2θ values of 12.4 , 24.8 , and 26.6 ; less
intense peaks at 2θ of 36.7 , 39.6 , 48.0 , 50.1 , and 60.1 ; and humps at
2θ = 19.8 –21.9 , 37.8 –39.2 , and 44.8 –46.9 , which are all associated with kao-
linite (K). Diffraction peaks of quartz (Q) could be found at 2θ values of 20.9 , 26.4 ,
50.9 , 62.3 , and 68.1 . Illite (I) was detected at 2θ = 17.9 , 30.2 , 35.1 , 42.4 , and
55 . Dickite (D) was also detected at 2θ = 12.23 , 35.66 , 55.55 , and 63.95 .
XPS Spectroscopy
Kaolin was also analyzed by XPS spectroscopy, which was performed using a
KRATOS AXIS ULTRA (Kratos Analytical, United Kingdom). It is one of the
16000
K
K : Kaolinite
Q : Quartz
I : Illite
12000 D : Dickite
Q
Intensity
8000
K
D Q K
4000
K
K I K
I K I KK I K
D K K Q ID QD
Q
0
0 10 20 30 40 50 60 70
Angle (2θ)
Fig. 4 Diffractogram RX of kaolin

reference techniques for the study of surfaces because the depth of analysis is a few
nanometers. The spectra give information on the chemical composition of the
surface of the materials. The source equipping the device is an X-ray source with
an aluminum/magnesium anode regulated in temperature and whose applied voltage
is set at 15 kV for a current of 20 mA. The surface of the crude kaolin was irradiated
by X-ray photoelectrons (Mg Kα source at 1253.6 eV, mid-height width of 0.7 eV)
under vacuum at 10-9 mbar. The general spectrum has a resolution of 0.5 eV. In this
case also, in order to facilitate the measurements, the sample is in the form of a pellet.
Figure 5 shows the complete XPS spectrum of the crude kaolin. A rapid exam-
ination shows essentially three peaks, one at 532.15 eV, the other at 102.85 eV, and
the last at 74.55 eV, respectively, attributed to the oxygen signals O1s, Si2p silicon,
and Al2p aluminum. Other compounds such as C, Ca, Na, F, and Mg are also present
but at low proportions. Given the nature of the clay, it seems natural to think that
carbon C comes from dried plants or insects and mix in powder form with the earth.
In order to learn more about the results of this clay, a finer analysis of the oxygen,
silicon, and aluminum peaks was undertaken. At high resolution, the O1s spectrum is
composed of a single O–Si peak at 532.101 eV (Fig. 6a), the Si2p spectrum is
Wide K08:1(K08 – Kaolinite–25–06–12)

XPS Spectrum Lens Mode:Hybrid Resolution:Pass energy 160 Iris(Aper):slot(SLOT)
x104
O 1s
48
40
Si 2s
Intensity(cps)
32 Ca2p
Na 1s Al 2s
Mg KLL
24
O KLL F 1s Si 2p
C 1s
16 Na KLL
Al 2p
8
O 2s
1000 800 600 400 200 0

Binding Energy (eV)
Fig. 5 Complete XPS spectrum of crude kaolin

O 1s K08:4(K08 – Kaolinite –25–06 –12)

a XPS Spectrum Lens Mode:Hybrid Resolution:Pass energy 20 Iris(Aper):slot(SLOT)
x102
O 1s K08
200
160
Intensity(cps)
120
80
40
540 536 532 528 524

Binding Energy (eV)
Si 2p K08:8(K08 – Kaolinite –25 –06 –12)

b XPS Spectrum Lens Mode:Hybrid Resolution:Pass energy 20 Iris(Aper):slot(SLOT)
x101
280 Si 2p K08
240
200
Intensity(cps)
160
120
80
40
112 108 104 100 96

Binding Energy (eV)
Fig. 6 (continued)
Al2p K08:9(K08 – Kaolinite–25 –06–12)

c XPS Spectrum Lens Mode:Hybrid Resolution:Pass energy 20 Iris(Aper):slot(SLOT)
x101
Al2p K08
100
80
Intensity(cps)
60
40
20
84 80 76 72 68
Binding Energy (eV)
Fig. 6 Deconvolution of the peaks O1s (a), Si2p (b), and Al2p (c) for the crude kaolin
Table 1 Contribution of different atoms in the kaolin spectrum

Pic Position (eV) Percentage atomic (%) Percentage mass (%)
Na1s 1072.55 0.92 1.11
F1s 685.15 0.34 0.34
O1s 532.15 61.38 51.43
N1s 401.95 0.23 0.17
Ca2p 351.85 0.61 1.29
C1s 284.65 9.12 5.74
K2p 293.20 0.65 1.34
Si2p 102.85 16.36 24.06
Al2p 74.55 9.49 13.41
Mg2p 50.05 0.88 1.13
composed of a single SiO2 peak at 102.856 eV (Fig. 6b), and the Al2p spectrum is
also composed of a single Al3+ peak at 74.57 eV (Fig. 6c).
In Table 1, we deferred the contribution of each of these elements to the total
kaolin signal (%).
Microscopy
Nanomorphology (backscattered electron images) and qualitative chemical analyses
of the kaolin samples were characterized by scanning electron microscopy (SEM)
and transmission electron microscopy (TEM). The SEM study was carried out using
Hitachi S-4800 equipped with energy dispersive spectrometry for chemical analysis
(EDS) and operating at 15 kV acceleration voltages. TEM study was performed with
a Philips CM200 microscope operating at 100 kV.
SEM micrograph of the untreated clay sample suggests a very cohesive material
(Fig. 7). The micrograph confirms that the material is forming micron-sized agglom-
erates. A higher magnification micrograph of the same structure shows that the
micro-sized particles are composed of individual platelets, which conglomerate
into larger-sized particles.
The obtained chemical analysis by energy dispersive spectroscopy (EDS) (Fig. 8)
shows the presence of framework Al and Si elements.
Some platelets with irregular semihexagonal rounding with hexagonal edges
were also observed, and the EDS spectrum shows that these small platelets constitute
Al, Si, Mg, Fe, Na, Ca, K, Ti, and O. These results confirm those found by the EDS
analysis which also revealed the presence of these elements in the form of oxides:
Al2O3, SiO3, Fe2O3, MgO, Na2O, CaO, K2O, and TiO2. The results of EDS analyzes
shown in Table 2 show that kaolin has a high percentage of oxygen, about 47.95%,
followed by silicon 28.71% and aluminum with 16.73%.
The TEM micrographs at low magnification showed (Fig. 9) a higher tendency of
the kaolin to aggregate.
Thermal Analysis
Thermal analysis of the kaolin samples was studied by thermogravimetry (TGA),
using the multi-module 92-10 Setaram analyzer. Analyses were carried out in the
temperature range 25–1000 C under air atmosphere, at a constant flow rate of
80 mL/min, in an alumina (Al2O3) crucible, and at a heating rate of 10 C/min. The
amount of sample analyzed was ~60 mg.
Fig. 7 SEM of kaolin clay
Si
3500
3000
Al
2500
2000
O
1500 Ti
Ca
1000 C
500
Mg
Cl K Ca
Na
Fe Cl K Ca Ti Ti Fe Fe
0 keV
0 5 10
Fig. 8 SEM-EDS spectra of kaolin sample
Table 2 Mass percentage of crude kaolin using X-ray energy dispersion (EDS)
Element C O Na Mg Al Si Cl K Ca Ti Fe Total
Weight % 0.20 47.95 1.00 1.4 16.53 28.71 0.55 2.20 0.46 0.34 0.51 100.00
Atomic % 0.08 61.85 0.81 1.30 12.80 21.09 0.32 1.16 0.24 0.15 0.19 100.00
Table 3 Chemical analysis of raw kaolin studying by comparing with another (weight %)
Element Al2O3 SiO2 TiO2 Fe2O3 CaO K2O MgO Na2O P2O5 SO3 LOF*
Kaolin 36.23 48.12 0.34 0.51 0.64 0.65 0.004 0.55 0.007 0.003 12.94
raw
Ideal 39.49 46.55 – – – – – – – – 13.96
kaolin
(Ekosse
2000)
*LOF: loss on fire
The TG of kaolin exhibited three stages of thermal decomposition. The first stage
was due to adsorbed water and occurred over a temperature interval of 25–200 C.
The second stage was related to the coordinated water and the partial loss of organic
moieties that were intercalated in the interlayer spacing over a temperature interval
of 300–500 C. The third loss over a temperature range of 500–1000 C was due to
the elimination of the organic groups and the dehydroxylation of the silanol groups
on the clay surface. The data exhibited a significant alteration in the thermal
degradation (see Fig. 10).
Fig. 9 TEM micrograph of

the kaolin
Fig. 10 TG analysis of 2
kaolin
0
−2
loss of mass (%)
−4
−6 Variation of mass : 9,891%
−8
−10
−12
100 200 300 400 500 600 700 800 900
Temperature (°C)
Fourier Transform Infrared (FTIR)

The Fourier transform infrared (FTIR) spectra using KBr pressed disk technique
were conducted by PerkinElmer Spectrum 2000 Infrared Spectrometer. Natural
maghnite and KBr were weighted and then were ground in an agate mortar for
10 min prior to pellet making. The spectrums were collected for each measurement
over the spectral range of 400–4000 cm1.
The FTIR spectra of the kaolin, in the range of 400–4000 cm1, were taken to
confirm the presence of functional groups that might be responsible for the adsorp-
tion process and presented in Fig. 11. As may be seen, clay displays a number of
adsorption peaks, reflecting the complex nature of the kaolin clay. The main bonds
observed were OH stretching, hydroxyl sheet at 3698 cm1 and 3620 cm1. H2O
stretching was also found at 1636 cm1. Bands at 1033 cm1 and 984 cm1 were
assigned to Si–O bonds in the SiO4 molecules (Martinez-Ramirez 2007).
76.7
70
2853.73
65
1635.91
60 2924.29
798.08
55 3698.88 694.81
3448.01 425.79
50 3651.73 3620.78
%T
45
912.97
40
35
535.30
30
1032.97
25
469.71
20.0
4000.0 3000 2000 1500 1000 400.0
cm−1
Fig. 11 IR spectrum of Kaolin
The other band at 913 cm1 was attributed to AlIV–OH vibrations (Cristóbal et al.
2010). The bands at 798 cm1, 750 cm1, and 694 cm1 were Si–O symmetric
stretching (Galan et al. 1996). Absorption at 535 cm1 was assigned as Si–O–AlVI,
where the Al is in octahedral coordination.
The data from several analytical techniques (XRD, chemical analysis, SEM,
TEM, EDX spectrum, XPS, infrared absorption spectroscopy, and thermal analysis
TGA) reveal that kaolinite is the dominant clay minerals. This clay is useful in
environmental protection by immobilizing pollutants.
The results of the XRD, XPS, and EDX analyses were quantitatively treated with
the Topas software (Bruker XAS) with a factor rwp = 16% and gives the following:
Functionalization of Kaolin with 3-Aminopropyltriethoxysilane

(APTES)
A composite material (modified clay) consists of several elementary components, the

combination of which confers a set of properties which none of the components,
taken separately, possess. The object which is most often sought by substituting a
composite material for a conventional material is for the same structural rigidity, an
appreciable gain in mass. Modified clay consists of two phases (the matrix and/or
reinforcement or load).
Chemical grafting of the organosilane on kaolin is less common. It consists in
creating covalent bonds between the organosilane and the kaolin. After hydrolysis,
the silanes converted to the silanols in turn react with the hydroxyl group of the clay
to form siloxanes (Le Pluart 2002).
20.0 g kaolin (dried at 105 C) was dispersed into 300 mL toluene by ultrasound
for 15 min. Then, 20.0 mL 3-aminopropyltriethoxysilane (APTES) was added
dropwise during vigorous stirring. The dispersion was refluxed at 100 C for 24 h.
The modified kaolin was centrifuged and washed with toluene, followed by volume
mixture between ethanol and distilled water (75/25 v%), respectively. The product
was dried at 105 C and sieved. The sketch in Fig. 12 shows the grafting process and
the structure of products.
The DRX diffractograms show that the modified kaolin has a peak d001 which has
been moved to the small angles 2θ of 5.96 for the raw kaolin (K08) at 4.63 for the
modified kaolin (KS); this results in an increase in the interlayer distance of the
kaolin from 1.48 to 1.91 nm.
Fig. 12 Different types of H 5C 2O

interaction between the OC2H5
surface of the clay and APTES H 5C 2O Si H
in toluene (a) hydrogen O
bonding, (b) proton transfer, +
and (c) an amine in the high
APTES Argile
position (Xue et al. 2011)
NH2
H 5C 2O H 5 C 2O
OC2H5 OC2H5
H5 C 2 O Si H 5 C2 O Si
NH2 NH3+
H
O O-
(a) (b)
NH2
Si OC2H5
O O
(c)
The SEM micrographs of raw Kaolin (K08) and modified kaolin (KS) were
illustrated in Fig. 13. Obviously, the layer structure remained fine after the organic
modification, and it could be observed that many small nanoparticles disappeared,
probably due to the gathering force after modification. The surface appearance was
slick for KS (b), much texture existed on the external surface layer pieces, and the
small nanoparticles could be caused by the grafting and bonding process of APTES,
which brought about a loose structure. KS showed a wide range of particle size,
which was probably resulted from part of the destroyed structure and the different
grafting degree during modification.
By EDS analysis we observed that there is an increase in the weight percentage of
the silica element (Table 4), this also confirms the grafting of APTES on the surface
of the kaolin.
The new band at 1400 cm1 of the modified kaolin indicates the deformation of
-NH, and the band which lies between 3317 and 3067 cm1 indicates the elongation
of -NH; these new bands confirm the presence of APTES on the kaolin. The
Fig. 13 (a) Photographic

board of kaolin (K08).
(b) Photographic board of
modified kaolin (KS)
Table 4 The percentage of Si of the raw and modified Kaolin

Element K08 KS
Si (weight %) 1% 28.71 32.52
absorption band at 2930 cm1 corresponds to the C–H stretching vibration of CH2
groups of APTES. These observations clearly indicate that the surface modification
of kaolin was carried out by APTES.
Thermogravimetric analysis generally shows that the first loss of mass, observed
at temperatures below 250 C and corresponding to the loss of water and APTES, is
less important for the organic clay sample than for the raw clay. On the other hand,
the second loss of mass at a temperature higher than 250 C is greater for organically
modified clays than for crude clay. In addition, the loss of mass recorded on the
kaolin (K08) is about 9.89% and 10.65% on the modified kaolin (KS).
Heavy Metals Removal by Adsorption
The metals of major environmental concern today are cobalt, nickel, copper, and
zinc. A few familiar methods in practice for removal of these and other metals are
chemical precipitation, ion exchange, solvent extraction, reverse osmosis, adsorp-
tion, etc. Reverse osmosis, although very effective, is a cost-prohibitive process as
the membranes get easily spoiled requiring frequent replacement. Chemical precip-
itation is not very suitable when the pollutants are present in trace amounts and also a
large amount of sludge is produced. Ion exchange is expensive and sophisticated.
Solvent extraction or electrolytic processes are also available, but they are consid-
ered to be cost-effective only for more concentrated solutions. The process of
adsorption has become one of the preferred methods for removal of toxic contam-
inants from water as it has been found to be very effective, economical, versatile, and
simple (Tran et al. 1999). Adsorption has the additional advantages of applicability
at very low concentrations, suitability for using batch and continuous processes, ease
of operation, little sludge generation, possibility of regeneration and reuse, and low
capital cost (Mohanty et al. 2006).
The processes have acquired global importance for minimization of the problem
of contamination of water and air, and these processes have become a significant
addition to green chemistry endeavors.
The current status of adsorption research for a variety of metals by geomedia
ranging from individual minerals to sediments and soils has been reviewed in a
recent volume edited by Jenne (Jenne 2007).
The different adsorption mechanisms and the factors affecting the uptake of
metals have been reviewed with respect to the effects of selected anions, competition
among metals, pH, metal concentration, loading, variable metal adsorption capacity,
ionic strength, etc. A variety of adsorption models have been briefly introduced with
a view to extend the laboratory studies to field.
Technical feasibility of using various low-cost adsorbents for heavy metal

removal from contaminated water has also been reviewed earlier (Babel and
Kurniawan 2003). Clay and their modified forms have received wide attention
recently for use as adsorbents of metal ions from aqueous medium because of their
easy availability and comparatively less cost.
The present study investigates the removal of Co(II), Ni(II), Cu(II), and Zn(II)
from aqueous solution using kaolin (K08) and modified kaolin with (3-aminopropyl)
triethoxysilane (KS). The present work aims to critically review information
concerning the factors that impact the adsorption and ion exchange, the system
kinetics, and equilibrium with respect to various models that have been applied in the
literature. Since both ion exchange and adsorption are usually involved in the uptake
of heavy metals by natural and modified clay, in the context of this work hereafter,
the term adsorption also includes the ion exchange that takes places. In practical
applications, adsorption and ion exchange can be grouped together as sorption for a
unified consideration.
A 0.2 g K08 and KS were placed in 20 mL solution of 100 mg/L and 200 mg/L,
respectively, of metal ion. The samples were equilibrated in shaker bath, operating at
25 C and 100 rpm. After a period of time, the supernatants were collected and quantified
for the amount of metal by SAA. The effects of the pH, the contact time, and the initial
metal ion concentration on the adsorption capacity of the K08 and KS were examined.
The maximum adsorption capacity was calculated from Langmuir and Freundlich
isotherms plot. The amount of metal ion adsorbed per unit mass of K08 and KS was
calculated by using the mass balance equation given in Eq. (2) (Mureseanu et al. 2011).
qe¼ðC0 Ce ÞV=m (2)
where qe is the maximum adsorption capacity in mg/g, C0 is the initial concentration,

Ce is the concentration at equilibrium of Zn(II) solution in mg/L, V is the volume of
the metal ion solution in mL, and m is the mass of the materials in grams.
Adsorption percentage (%) was derived from the difference of the initial concen-
tration (C0, mol/L) and the final one (Ce, mol/L) (Eq. (3)):

C0 Ce
Sorption% ¼ 100 (3)
C0
Langmuir and Freundlich isotherm models were used in this study to establish the
relationship between the amount of adsorbed metal onto clays and its equilibrium
concentration in aqueous system.
Langmuir adsorption isotherm (Langmuir 1918) is based on the assumption of
monolayer adsorption onto a surface with a finite number of identical sites. Lang-
muir isotherm could be arranged in its linear form as following (Eq. (4)):
Ce Ce 1
¼ þ (4)
qe qm K L qm
where Ce is equilibrium concentration of the metal (mg/L) and qe is the amount of the
metal adsorbed per gram of adsorbent (mg/g). qm and KL are Langmuir constant
relating adsorption capacity (mg/g) and the energy of adsorption (L/g), respectively.
These constants can be calculated from the slope and intercept of the linear plots of
Ce/qe versus Ce, respectively.
The adsorption data were also fitted to Freundlich isotherm (Freundlich 1906),
which is described by the linear form following the equation (Eq. (05)):
logqe ¼ logK F þ nlogCe (5)
where KF and n are Freundlich constants, determined from the intercept and slope of
the linear plot of logqe versus logCe.
Cobalt
The raw kaolin K08 and modified kaolin KS has much potential as an adsorbent for
the removal of Co(II) ions from effluents. The time, sorbent dose, and temperature
proved to be important parameters on the sorption process.
The effect of contact time on the adsorption of cobalt on raw kaolin K08 and
modified kaolin KS was investigated in order to determine the minimum necessary
time to achieve the sorption equilibrium. The experiment was performed at an
optimum pH of 6.96. Optimum adsorption of cobalt was achieved sharply within
the first 6 minutes remaining fairly stable thereafter.
The fast initial uptake reflects the accumulation of cobalt ions on the surface and
the availability of abundant active sites on the surface of the clay. The adsorption
process slows down with time as the active sites were used up. The fast metal uptake
observed is of particular importance in process design and operation in practical uses.
The kinetic study revealed that the pseudo-second-order model was appropriate in
describing the adsorption process. The linearity of the plot is indicated by R2 = 0.99;
this shows the applicability of the model for this sorption process.
The pseudo-second-order model is based on the assumption that adsorption
follows a second-order mechanism, so the rate of occupation of adsorption site is
proportional to the square of the number of unoccupied site (Zafar et al. 2006)
(Tables 5 and 6).
Nickel
From this study of the Ni adsorption rate by raw kaolin K08 and modified kaolin KS,
the results indicate that the equilibrium condition occurred within 6–12 h. The
adsorption isotherms can satisfactorily be described by both the Freundlich model.
The modified kaolin KS by APTES displayed the highest adsorption capacity, while
raw kaolin K08 provided the lowest adsorption capacity.
Table 5 Langmuir and Freundlich isotherm parameters for adsorption of Co(II) onto raw kaolin
(K08) and modified kaolin (KS)
Cobalt
Ni(II) (pH = 6.96, t = 6 min, T = 25 C, C0 = 100–200 mg/L)
Sample Langmuir isotherm constants Freundlich isotherm constants
Qe (mg/g) KL (L/g) R2 n KF R2
Raw kaolin (K08) 7.29 0.02 0.993 3.08 1.36 0.840
Modified kaolin (KS) 18.79 1.23 0.997 1.24 2.68 0.798
Table 6 The pseudo-first-order and the pseudo-second-order parameters for Co(II) onto raw and
modified kaolin
Pseudo-first order Pseudo-second order
k1 qe calculated K2 (g.mg1. qe calculated
Sample (min1) (mgg1) R2 min1) (mgg1) R2
Raw kaolin 1.74 4.16 0.899 0.37 6.53 0.992
(K08)
Modified 2.21 7.26 0.856 1.25 17.54 0.989
kaolin (KS)
Several parameters such as pH, adsorbent dose, contact time, and initial metal ion
concentration influenced the adsorption process. The adsorption equilibrium was
attained at 10 min, and adsorption efficiency reached a maximum of 87.30% at optimal
pH of 7.5, adsorbent dose of 1 g/L, and initial metal ion concentration of 100 mg/L. The
results of the study conclusively proved the effectiveness of modified kaolin KS as an
adsorbent for Ni (II) removal from aqueous solution. The adsorption capacity depends
significantly upon the specific surface area of the clay (Tables 7 and 8).
Copper
In this study, firstly, we used raw kaolin K08 and modified kaolin KS by grafting the
APTES, in which adsorption of copper from standard CuSO4.5H2O solutions was
investigated. Secondly, optimal adsorption conditions were analyzed. It was
observed that the maximum copper removal was at the pH 5.5 for both raw kaolin
K08 and the modified kaolin KS. The adsorption is too fast at the first 30 min of
contact time for the modified kaolin KS. The rapid removal of the adsorbate has
significant practical importance as it will facilitate smaller reactor volumes ensuring
efficiency and economy.
It is observed that the degree of adsorption increases with increasing temperature,
and maximum adsorption of copper ions is obtained at 30 C which is the temper-
ature of the solution for the modified kaolin KS.
Thirdly, isotherm data of Cu2+ adsorption on K08 and KS were calculated. Based
on the correlation coefficient values, it has been deduced that the Langmuir and
Freundlich isotherms are suitable for fitting the experimental findings.
Table 7 Langmuir and Freundlich isotherm parameters for adsorption of Ni(II) onto raw kaolin
Nickel
Ni(II) (pH = 7.5, t = 10 min, T = 25 C, C0 = 100–200 mg/L)
Raw kaolin (K08) 7.69 0.04 0.991 3.45 1.38 0.940
Table 8 The pseudo-first-order and the pseudo-second-order parameters for Ni(II) onto raw and
modified kaolin
Raw kaolin 0.31 4.19 0.866 3.22 6.23 0.999
(K08)
Modified 0.80 5.32 0.796 2.36 18.31 0.995
kaolin (KS)
The high correlation coefficient showed that the Langmuir adsorption isotherm
model is suitable for describing the adsorption equilibrium of copper ions. The
investigation showed that the K08 and KS are very valuable material for the removal
of copper ions from aqueous solutions. In addition, the use of the raw kaolin K08 and
modified KS by APTES for the removal of copper ions from the aqueous solutions
can potentially reduce the remediation costs (Tables 9 and 10).
Zinc
In this study, removal of Zn2+ is investigated using raw kaolin K08 and modified
kaolin by APTES. Total metal (Zn) removal percentage as high as 89.22% could be
obtained, when the initial solution (Zn) concentration is used on its higher level
(100 mg/L) and the degree of agitation is at the lower level (100 rpm). It was also
observed that, for the absolute capacity of removal (qm), the best results were
obtained in tests performed with higher (100 mg/L) concentration, the best result
being a total of 12.23 mg for K08 and 18.56 mg for KS of Zn removed for every
gram of clay (see Table 11). The adsorption isotherms were better represented by the
Langmuir model for the process.
Using the study of the kinetics of removing zinc, in a finite bath system, by kaolin
and modified kaolin, it was verified that the equilibrium time is reached after the
elapse of 40 min and the percentage removal of zinc was 86.39%.
The value of the velocity constant obtained by the model was 11.33 (g.mg1.
min1) for raw kaolin and 2.35 (g.mg1.min1) for modified kaolin, that of the
amount of Zn adsorbed was 9.44 (mg/g) for raw kaolin and 14.28 (mg/g) for
Table 9 Langmuir and Freundlich isotherm parameters for adsorption of Cu(II) onto raw kaolin
Copper
Cu(II) (pH = 5.5, t = 30 min, T = 25 C, C0 = 100–200 mg/L)
Raw kaolin (K08) 9.17 0.06 0.993 3.55 1.91 0.928
Table 10 The pseudo-first-order and the pseudo-second-order parameters for Cu(II) onto raw and
modified kaolin
Raw kaolin 0.27 5.35 0.958 0.25 7.41 1
(K08)
Modified 1.69 6.25 0.896 1.25 21.59 0.995
kaolin (KS)
Table 11 Langmuir and Freundlich isotherm parameters for adsorption of Zn(II) onto raw kaolin
Zinc
Zn(II) (pH = 6.1, t = 40 min, T = 25 C, C0 = 100–200 mg/L)
Raw kaolin (K08) 12.23 0.32 0.988 1.82 2.7 0.981
Table 12 The pseudo-first-order and the pseudo-second-order parameters for Zn(II) onto raw and
modified kaolin
Raw kaolin 0.18 0.07 0.855 11.33 11.44 1
(K08)
Modified 0.32 9.24 0.654 2.35 23.98 0.999
kaolin (KS)
modified kaolin and the adjustment for the correlation coefficient of the model was
1 and 0.9999, respectively (see Table 12).
The process for removing zinc using modified kaolin by APTES proved to be
adequate and highly efficient.
Conclusion
Isotherm studies have been conducted for adsorption of Co, Ni, Cu, and Zn using
raw kaolin K08 and modified kaolin KS.
Raw kaolin obtained from Algerian quarries manifested acceptable adsorption
performance regarding the removal of low-concentration metal ions, namely,
Co(III), Ni(II), Cu(II), and Zn(II), in polluted water.
Adsorption of Co(II), Ni(II), Cu(II), and Zn(II) on all clay samples kaolin K08
and modified kaolin KS follows Langmuir isotherm.
The second-order kinetic model represented well the mechanism of interaction
involved during Co, Ni, Cu, and Zn adsorption into the pores of the raw kaolin K08
and modified kaolin KS.
The modified kaolin KS by APTES had detrimental effect on adsorption perfor-
mance of kaolin as compared to its raw form. However, the low-grade raw kaolin
used in the present study was found to be an effective cheap source of scavenging
material for heavy metal removal.
Almost all samples (K08 and KS) showed adsorption capacity in the order of
Zn > Cu > Ni > Co.
Kaolin used in this work represents a cheap and viable option for the removal of
low-concentration metal ions from polluted water.
Acknowledgments The authors gratefully acknowledge Dr. Yves Pillet (Faculty of Sciences and
Technology, group PGCM, University of Lorraine, Nancy, France) because of his contribution to
our study and are thankful for Joint Service Electronic Microscopy and Microanalysis at the
University Henri Poincare of Nancy for MEB-EDS analysis.
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Concept Note on Method Development
for Speciation and Measurement of 48
Arsenic (As) in Its Valence States (As (III)
and As (V)) in Solid and Semisolid
Organic Environmental Samples
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1192
Experimental Approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1193
Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1193
Sample Pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1193
Speciation of As (III) and As (V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1193
Work Plan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1195
Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1195
Treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1196
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1197
Abstract
Arsenic, a metalloid widely distributed in nature, is released into the environment
from a wide range of sources. Its toxicity and carcinogenicity mainly result from
its trivalent form rather than its pentavalent state. This makes the speciation and
measurement of arsenic in its valence states extremely important for assessing
potential health hazard. Arsenic speciation methods exist for natural water sam-
ples. However, for solid samples it is often the total arsenic content that is
measured. This chapter lays out a concept note on method development for
speciation and measurement of arsenic in its valence states (i.e., As (III) and
As (V)) in solid and semisolid organic environmental samples. The concept is
A. M. M. M. Hossain (*)
School of Global, Urban and Social Studies, College of Design and Social Context,
RMIT University, Melbourne, VIC, Australia
Center for Integrated Knowledge Invention, Laverton, VIC, Australia
e-mail: maruf.hossain@integratedknowledgeinvention.com

https://doi.org/10.1007/978-3-319-73645-7_159
1192 A. M. M. M. Hossain
based on chemical extraction of As (III) and As (V) species through respective

precipitation followed by their dissolution into solution phase, which could be
measured through “high-performance liquid chromatography inductively coupled
plasma mass spectrometry” (HPLC/ICP-MS). Experimental approaches and
work plan on this concept have also been elaborated.
Keywords
Arsenic · Arsenic (III) · Arsenic (V) · Speciation method · Environmental
samples
Introduction
Arsenic (As) is widely distributed in nature (in Earth’s crust at 2–5 mg/Kg (Onishi
and Sandell 1955)), and is classified as metalloid, i.e., occurring both in solid and
liquid states (Carson et al. 1986). It is released into the environment from a wide
range of sources including industrial processes (such as use in hardening lead, in
glass manufacturing, in electrical devices), during power generation from coal-
fired furnace, from use in agricultural and silvicultural products, as well as as feed
additive for livestock. As the toxicity and carcinogenicity of arsenic mainly result
from exposure to its trivalent form, i.e., As (III), rather than its pentavalent state,
i.e., As (V) (Costa 2000), there is a necessity of measuring arsenic species in a
given sample instead of simply determining total arsenic content in that sample.
Liquid chromatographic methods exist for measuring arsenic species in natural
waters, such as the HPLC/ICP-MS technique (ISO/IEC 2005; Komorowicz and
Baralkiewicz 2014). However, solid and semisolid samples cannot be measured
using similar method. For solid samples it is often the total arsenic content that is
measured (primarily through acid digestion, such as the method described by FDA
(2015)) in assessing the corresponding arsenic hazard. As As (III) is mostly
responsible for arsenic toxicity, a concept note is developed in this article towards
method development for speciation and measurement of arsenic in its valence
states (i.e., As (III) and As (V)) in solid and semisolid organic environmental
samples.
This concept note is intended for organic environmental samples as it is not
possible to measure arsenic contents in soils and sediments without destroying
their lattice structure that involves digestion method, rendering the sample
unsuitable for speciation and measurement of ions in different valence states.
This is due to the alterations that occur in relative abundance of ions through
oxidation reaction, resulting in As (III) turned into As (V). This concept note is
based on avoiding acid digestion in order not to disturb the natural relative
abundance of As (III) and As (V) in the samples, and instead through inducing
definitive chemical reactions that can extract and isolate As (III) and As (V) for
their determination.
48 Concept Note on Method Development for Speciation and Measurement of. . . 1193
Experimental Approaches
Sampling
The in situ-collected samples ought to be kept in airtight condition in order to

prevent sampling substance modification through oxidation, and be quickly trans-
ported to laboratory for analysis. The sample treatment and analysis are to be carried
out in original condition (i.e., raw weight basis) while the dry weight coefficient is to
be determined and adjusted from a separate portion of the sample.
Sample Pretreatment
The solid samples are to be ground into small pieces in order to expose the maximum
possible surface areas of the sample matrix, and be analyzed as soon as the grinding
is complete in order to prevent alteration of the redox condition of sample matrix
through oxidation from air.
Speciation of As (III) and As (V)
Step 1 Arsenic present both as As (III) and As (V) compounds or As3+ and As5+ ions in
organic solid or semisolid samples in absorbed, adsorbed, or free state form that can be
precipitated as arsenic (III) sulfide and arsenic (V) sulfide through use of hydrosulfuric
acid in cold acid (hydrochloric) solution. As in neutral or basic condition the
hydrosulfuric acid would undergo no reaction with As (III) and As (V) compounds,
hence no precipitate of arsenic (III) sulfide and arsenic (V) sulfide; it is necessary to
maintain acidic condition in the medium for the reaction to occur. Although the color of
both of the precipitates is yellow, due to similar potential reaction occurring with other
compounds present in the sample matrix can yield precipitates of various colors, hence
interfering with the color of arsenic (III) sulfide and arsenic (V) sulfide precipitates.
As ðIIIÞ compound þ3H2 S þ 6HCl! As2 S3 # þ6NaCl þ 6H2 O

ðSuch as 2Na3 AsO3 Þ ðYellow precipitateÞ
2½AsCl4 þ 3H2 S !
acid medium
As2 S3 # þ8Cl þ 6Hþ
ðYellow precipitateÞ
2AsO2 þ 5H2 S ! þ2HS

acid medium
As2 S3 # þ 4H2 O
acid medium
2HAsO2 þ 3H2 S ! As2 S3 # þ4H2 O
cold, HCl medium

As ðVÞ compound þ5H2 S ! As2 S5 # þ8H2 O
ðSuch as 2H3 AsO4 Þ ðYellow precipitateÞ
Step 2 The precipitate is to be filtered together with the sample residue, and dried
with filter paper. If the mass is to be washed with water in order to remove any
water-soluble impurities, a correction factor must be introduced to account for the
solubility of arsenic (III) sulfide and arsenic (V) sulfide precipitates. For example,
the solubility of arsenic (III) sulfide in water is 5 105 g/100 mL (i.e., 0.5 mg/L).
The filtered solution phase is to be kept for checking any presence of arsenic
through applying acid digestion method (FDA 2015). This accounts for arsenic
(if any) released from the sample into the solution phase instead of forming
precipitate.
Step 3 Both of the arsenic (III) sulfide and arsenic (V) sulfide precipitates are
readily soluble in solutions of alkali hydroxides, ammonium hydroxide, and ammo-
nium sulfide.
LiOH∕ NaOH∕ KOH in

aqueous medium AsO2 þ 3AsS2
2As2 S3 þ 4OH ! þ 2H2 O
ðDissolved in colorless solutionÞ
AsO2 þ 3AsS2
2As2 S3 þ 4NH4 OH! þ 2H2 O þ 4NH4 þ
As2 S3 þ 3S2 !2AsS3 3
LiOH in
aqueous medium 3AsO4 3 þ 5AsS4 3
4As2 S5 þ 24OH ! þ 12H2 O
3AsO4 3 þ 5AsS4 3
4As2 S5 þ 24NH4 OH! þ 12H2 O þ 24NH4 þ
As2 S5 þ 3S2 2 !2AsS4 3 þ 3S
In this step, the filtered mass containing arsenic (III) sulfide and arsenic (V) sulfide
precipitates is to be mixed with ammonium hydroxide or lithium hydroxide
(in aqueous medium), which would dissolve both of the precipitates into liquid
phase. This should separate the As (III) and As (V) species from solid phase (i.e.,
filtered mass) and integrate them into the solution phase. Although the dissolution of
arsenic (III) sulfide and arsenic (V) sulfide should produce a colorless solution,
potential mixture of some other colors could also occur due to dissolution of some
other precipitates present in the filtered mass.
The solution phase is to be filtered and collected for subsequent step, while the
remaining solid residue is to be kept for checking any yet uncollected arsenic content
through applying acid digestion method (FDA 2015).
Step 4 The solution collected from step # 3 would contain As (III) as AsO2 and
AsS2, and As (V) as AsO43 and AsS43. These As (III) and As (V) species could
be measured through high-performance liquid chromatography inductively coupled
plasma mass spectrometry (HPLC/ICP-MS) as described by Komorowicz and
Baralkiewicz (2014).
Work Plan
The work plan on this concept needs to individually study all representative
chemical reactions at sufficient details so that the efficiency and best working
range for each step could be ascertained. The impacts of various factors for
common sample types also need to be studied for the optimization of working
procedures.
Sampling
There should be two types of samples: theoretical and environmental samples.
Theoretical Samples
The theoretical samples include four pure-grade arsenic compounds as described in
Table 1.
Table 2 studies the solubility of the theoretical arsenic sample compounds in
acids, bases, and aqueous medium.
Environmental Samples
• Primary samples: Heavily arsenic-contaminated organic environmental samples
• Secondary samples: Plant- and animal-sourced organic samples such as vegeta-
bles, fruits, crops, meat, dairy, and egg
• Tertiary samples: Other organic solid and semisolid environmental samples
There is no pretreatment required for the theoretical samples, while the pretreatment
for the environmental samples should be the same as described in section “Sample
Pretreatment.”
Table 1 List of theoretical samples

[Oxidation state + 3] [Oxidation state + 5]
As3+, AsO2, AsO33 ions As5+, AsO43, As2O74
Name (colorless) (colorless)
Arsenic oxide As2O3 (white color) As2O5 (white color)
Arsenic sulfide As2S3 (yellow color) As2S5 (yellow color)
Table 2 Solubility Solubility

observation table for Oxidation in H2O Solubility Solubility
theoretical arsenic state Compound (g/100 mL) in acids in bases
sample compounds
+3 As2O3
+5 As2O5
+3 As2S3
+5 As2S5
Treatments
Theoretical Arsenic Speciation

The following treatments are to be conducted for each of the theoretical arsenic
sample compounds:
1. As in sample: H2S: HCl ratio
1 mole:3 moles:6 moles

Result As (III) and As (V) species must be in the precipitate, which can be
confirmed through analyzing the filtered solution phase for total arsenic. The highest
precipitate weights should be forwarded to the subsequent step.
2. [As in precipitate: NH4OH] and [As in precipitate: LiOH]
1 mole:2 moles (conc.) 1 mole:2 moles (aqueous)

Result As (III) and As (V) species must be in the solution phase, which can be
confirmed from observing no precipitate, or analyzing the precipitate (if any) for
total arsenic. The treatments resulting in complete solution or the solutions with the
least precipitates—after confirming any arsenic presence in the precipitate—should
be taken for As (III) and As (V) species measurement through HPLC/ICP-MS
(Komorowicz and Baralkiewicz 2014).
Empirical Total Arsenic

The theoretical arsenic sample compounds are to be acid digested (FDA 2015) to
measure empirical total arsenic, which is to be compared with the sum of the
determined As (III) and As (V) species for verifying the efficiency of the speciation.
Arsenic Speciation in Environmental Samples

The optimum ranges of reaction conditions observed for theoretical arsenic specia-
tion are to be utilized to study the speciation efficiency for all three types of organic
environmental samples. This includes measuring empirical total arsenic for each
sample type in order to determine the extent of arsenic retrieved through the
speciation method, and following through any further improvements necessary for
improving the efficiency of the method including optimization for each sample type.
References
Carson BL, Ellis HV, McCann JL (1986) Toxicology and biological monitoring of metals in
humans: including feasibility and need. Lewis Publishers, Chalsea
Costa M (2000) Trace elements: aluminum, arsenic, cadmium, and nickel. In: Lippmann M
(ed) Environmental toxicants: human exposures and their health effects, 2nd edn. Wiley,
Hoboken, pp 811–850
FDA (2015) Elemental analysis manual for food and related products, Section 4.7: Inductively
coupled plasma-mass spectrometric determination of arsenic, cadmium, chromium, lead, mer-
cury, and other elements in food using microwave assisted digestion. United States Food and
Drug Administration. https://www.fda.gov/downloads/food/foodscienceresearch/laborator
ymethods/ucm377005.pdf. Accessed 23 Sept 2017
ISO/IEC 17025:2005 (2005) General requirements for the competence of testing and calibration
laboratories
Komorowicz I, Baralkiewicz D (2014) Arsenic speciation in water by high-performance liquid
chromatography/inductively coupled plasma mass spectrometry-method validation and uncer-
tainty estimation. Rapid Commun Mass Spectrom 28:159–168
Onishi H, Sandell EB (1955) Geochemistry of arsenic. Geochim Cosmochim Acta 7:1–33
Determination of Select Heavy Metals
in Air Samples from Aurangabad City 49
Onkar Jogdand, N. N. Bandela, Geetanjali Kaushik, and Arvind Chel
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1200
Study Location . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1202
Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1203
Chemical Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1204
Meteorological Observations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1204
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1206
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1207
Abstract
Living organisms require trace amounts of certain heavy metals, including cobalt,
copper, manganese, molybdenum, strontium, and zinc but excessive levels can be
detrimental to the organism. Other heavy metals such as mercury, lead, and
cadmium are known to have vital impact on organisms; however, their accumu-
lation over time in the bodies of mammals can cause serious illness. The partic-
ulate heavy metals can have severe toxic and carcinogenic effect for humans
when inhaled in higher concentration. Therefore monitoring of heavy metals
present in particulate matter is an important environmental issue. In this work,
the atmospheric concentrations of selected heavy metals including Lead (Pb),
Cadmium (Cd), Nickel (Ni), Manganese (Mn), and Zinc (Zn) were measured for
O. Jogdand · N. N. Bandela
G. Kaushik (*) · A. Chel
Maharashtra, India

https://doi.org/10.1007/978-3-319-73645-7_164
1200 O. Jogdand et al.
different sampling sites in Aurangabad city of Maharashtra. High volume air

samplers and glass fiber filters were used to collect the samples. The collected
samples were digested using a mixture of analytical grade hydrogen fluoride and
analyzed to evaluate the levels of heavy metals by Atomic Absorption Spectro-
photometry. Five heavy metals (Pb, Ni, Mn, Cd, and Zn) were monitored.
Locations namely Kranti Chowk, Railway Station, Waluj Industrial area, SB
College, Gulmandi Chowkand Harshul T Point have revealed high concentrations
of selected heavy metals. To determine the emission sources of these metals, it is
recommended to undertake more detailed and comprehensive study.
Keywords
Heavy metals · Air pollution · Atomic absorption spectrophotometer · Particulate
matter · Filters
Introduction
World over air pollution is a public health problem. In 2012 air pollution was
declared as the largest environmental health risk with almost seven million deaths
globally attributed to it (WHO 2014). Data from India’s major regulator the Central
Pollution Control Board (CPCB) revealed that 77% of Indian urban clusters clearly
exceeded the National Ambient Air Quality Standard (NAAQS) for respirable
suspended particulate matter (PM10) in 2010 (CPCB 2014). It is quite alarming to
note that the satellite measures of fine particulates created for the entire India reveal
that our populations living both in urban and rural areas are exposed to hazardously
high levels of particulates. Almost 670 million people comprising 54.5% of the
population reside in regions that do not meet the Indian NAAQS for fine particulate
matter (Greenstone et al. 2015; Dey et al. 2012). Numerous studies have revealed a
consistent correlation for particulate matter concentration with health than any other
air pollutant. Studies show a statistically significant correlation between mortality
and ambient particulate matter concentration (Lee et al. 2006).
Particulate Matter (PM) refers to tiny particles which remain suspended in air, in
the form of either solid or liquid droplets which originate from various sources that
pollute the ambient air.
Particulate matter comprises of various organic and inorganic components; the major
components include acids, ammonia, sodium chloride, black carbon, water, and mineral
dust. These respirable particulates having aerodynamic diameter 10 μm (PM 10) are
an important part of the atmosphere. These particles have a high probability of deposi-
tion deeper into the respiratory tract and are likely to trigger respiratory diseases such as
asthma, bronchitis, cardiopulmonary infections (Apte et al. 2011; WHO 2014).
These particles have also been implicated as carriers of toxic air pollutants
including heavy metals and organic compounds (Satsangi et al. 2011).
Particulate heavy metals can have severe toxic and carcinogenic effect for humans
when inhaled in higher concentration (Panne et al. 2001). Living organisms require
trace amounts of some heavy metals, including cobalt, copper, manganese,
49 Determination of Select Heavy Metals in Air Samples from Aurangabad City 1201
molybdenum, strontium, and zinc, but excessive levels can be detrimental to the
organism. Other heavy metals such as mercury, lead, and cadmium are known to have
vital or beneficial effect on organisms, and their accumulation over time in the bodies
of mammals can cause serious illness (Srivastava and Majumder 2008; Hsan 2008).
The main input for many elements in the atmosphere is related to particle emission
processes. Regarding trace metals (Pd, Cd, Zn) anthropogenic sources play a more
significant role than natural sources, such as continental dust, salt spray, and biogenetic
particles (Silvia et al. 2004; Katja et al. 1998; Figen et al. 2000; Munir and Shaheen 2008).
Atmospheric metal concentration shows spatial variation since they are dependent on the
distances to the sources and of the relative importance of local sources. Seasonal variation
has been observed in atmospheric metal concentration in temperate or cold climates, but
their levels are also influenced by meteorological variables such as wind speed and
direction. Short-term differences of atmospheric metal concentration have been observed
in a day-to-day or even an hour-to-hour basis (Munir and Shaheen 2008).
Trace quantities of heavy metals are found in fossil fuels, and they are released
into the atmosphere following combustion processes, including power generation
and emissions from vehicles. Industrial processes, including the manufacture of steel
and iron, and other metallurgical and chloralkali industries are also significant
sources of heavy metals. Different industries release different metals, for example,
lead emissions, which were previously almost completely from road transport, are
now dominated by processes in the iron and steel sector. The largest source of arsenic
is the burning of wood which has been treated with copper-chrome arsenate.
Noncombustion sources of heavy metals include demolition of buildings, corrosion
and abrasion of sources such as road surfaces, tire and brake wear.
It is important to note that in addition to these anthropogenic sources, heavy
metals are also released into the atmosphere from natural sources including volca-
noes, forest fires, sea-spray, and windblown soil particles. As they are chemical
elements, heavy metals do not degrade. This means that any metals which are
released to the environment have the potential to become resuspended in the atmo-
sphere, for example, windblown particles of soil and road dust (Arora et al. 2017).
Several heavy metals have been determined in air samples in different countries
such as Brazil (Silvia et al. 2004), Denmark (Karl et al. 2002), Portugal (Vasconcelos
and Tavares 1997), India (Khillare et al. 2004), Spain (Moreno-Grau et al. 1997,
2000; Mateu et al. 1999), Egypt (Abdel-Shafy et al. 1992), and Russia (Drobyshev
and Emelina 2001), not to mention national and international continuous monitoring
programs for regulatory purposes like the European Monitoring and Evaluation
Program. Various studies have been reported in the literature regarding heavy
metal concentrations in air within Indian cities (Pandit et al. 2013; Jha 2010;
Singh et al. 2008; Dubey et al. 2012; Gupta and Karar 2006).
The main aim of this research is to determine the levels of heavy metals including
Pb, Ni, Mn, Cd, and Zn in air samples collected from 19 different sites in Aurang-
abad city, then compare the levels of heavy metals in the various sites, and deduce
causes for the presence of the heavy metals in air within the study area. To the best of
our knowledge this study would be the first to provide valuable preliminary data on
ambient concentrations of heavy metals in Aurangabad city.
Study Location
Aurangabad city in Maharashtra is the site of headquarters of Marathwada region

(Fig. 1). It has a rich historical background and is a popular tourist place for both
domestic and international tourists. The city is situated at a latitude of 19 530 5900
North and longitude 75 200 East. Aurangabad’s area is about 138 km 2.The climate of
Marathwada region is generally hot and dry. The average temperature for day ranges
from 27.7 C to 38.0 C while it ranges from 26.9 C to 20.0 C during the night.
Average annual rainfall in the city and adjoining areas is 725.8 mm while the relative
humidity is extremely low in this region for a major part of the year and ranges
between 35% and 50%, while it is the highest (85%) during monsoon. The total area
under forest cover is about 557 km2 which comprises of only 7.6% area of the total
land area in Aurangabad (Kaushik et al. 2016). Recent census data revealed that the
population of the city is about 1,500,000 (AMC 2011).The city boasts of a total
number of industrial units (small-, medium-, and large-scale) as about 1020, and
almost 35,000 workers find their employment in these units (Bhosale et al. 2010).
The rapid industrial growth of Aurangabad has resulted in urbanization of the city and
has also increased air pollution. The number of vehicles has also increased making a
significant contribution to the vehicular traffic. The sampling sites according to their
different land use patterns, populations, and traffic densities have been selected for
monitoring particulate matters. The measurements of PM10 have been carried out on
the terrace of the building (above 3–5 m above the ground) at each site (Table 1).
Fig. 1 Location of
Aurangabad city (Latitude
19 530 5900 North and
Longitude 75 200 East)
(Source: Environment Status
Report Aurangabad
(2013–2014))
Table 1 Location of monitoring sites

Traffic Land use
Location Description density pattern
1. Seven Hill Near to Flyover and commercial complex High Mixed
2. Doodh Site of office of government entity, MSEDCL High Commercial
Dairy
3. Gulmandi Busy densely populated market area Medium Mixed
4. Kranti Near to Flyover and commercial complex High Commercial
Chowk
5. (MIDC) Open industrial area with only few units Medium Industrial
Chikalthana functioning
6. CIDCO – City bus stand buzzing with commuters and bus High Commercial
Bus stand drivers and cleaning staff
7. Mill corner City Police Commissioner Office High Mixed
8. Railway City Railway Station with high rush of visitors and High Commercial
Station also the residents
9. Harsul T Outskirt of city interstate buses, vans pass through High Mixed
Point the area
10. JNEC – Educational institution with around 8000 students Medium Institution
MGM campus and 500 faculty members
11. SB College, Unpaved roads High Mixed
Aurangpura
12. Airport, Airport is on city outskirts, large open area Low Airport
Chikalthana
13. TV Center Government TV transmission center High- Mixed
medium
14. City Densely populated residential area with market Medium Mixed
Chowk
15. MIDC – Over 1200 industries High Industrial
Waluj
16. Beed City outskirts where vehicles meant for other High Commercial
bypass locations bypass the city. Heavy truck traffic
17. Gajanan Center of city, densely populated High Mixed
Mandir
Chowk
PM10 monitoring was carried out in selected city locations during December,
2015–January, 2016. The samples were collected for 24 h. PM10 samples were
collected on Whatman filter papers with the help of a Respirable Dust Sampler
(Model – APM 460 DXNL, Envirotech, New Delhi). The high volume sampler was
operated at a flow rate of 1.1 m3/min. Field blanks were also collected.
Before beginning the sampling all the filter papers were preweighed with the help
of a Metler analytical weighing balance. Then the filter papers were desiccated for
the duration of 24 h. In order to avoid any sort of contamination, conditioned and
preweighed filter papers were kept in a zip lock polybag for taking to the field for
sampling. Prior to loading the filter papers on the sampler, the initial manometer and
timer readings were noted. Subsequently the filter papers were loaded on the sampler
and after ensuring that the sampler was properly screwed the sampler was started.
At the end of sampling period, the loaded filter paper was removed with the help of
forceps, wrapped in aluminum foil, and placed in a zip lock polybag. In the
laboratory the filter paper was conditioned and was again weighed to determine
the PM10 mass concentration (Satsangi et al. 2011).
Chemical Analysis
A portion (100 cm2) of the filter sample was cut into small pieces with stainless steel
scissors before being subjected to digestion. Papers were then digested. HF was added
and the beaker was covered with a watch glass, then the mixture was heated to near
dryness at the hot plate. The sample was allowed to cool to room temperature, then
transferred into a 100-mL volumetric flask and diluted to volume with distilled water.
The heavy metal concentrations were determined by flame atomic absorption
spectrometry with air/acetylene burner. Each result is the average of three readings.
Meteorological Observations
During the air quality monitoring the wind direction (WD) and speed (WS), tem-
perature, relative humidity (RH), and the rainfall were also recorded. The average
minimum and maximum temperatures were 14 C and 30 C. Average minimum and
maximum RH were 26 and 51, while the prominent WD was East with WS ranging
from 6 to 14 km/hr. During the period of sampling there was no rainfall (IMD 2016)
(Table 2).
The mean quantity of Ni in PM10 of different selected sites was in order of Cidco
bus stand > Kranti Chowk > Seven Hill > Harshul T Point > SB College.
Concentration of Ni was found highest at Cidco bus stand site probably due to
high vehicular movements. In a similar manner Kranti Chowk, Seven hill, and
Harshul T Point have a high Ni concentration owing to high vehicular traffic.
Use of Ni for plating the external part of a motor vehicle and as a fuel additive
may be a probable source of Ni in the atmosphere.
At six other locations Nickel was found below the detection limit. The higher
concentration at Harshul T Point is due to a combination of transportation and civil
construction work impact in this area.
Table 2 Heavy metal concentrations
r.No. Sampling locations Nickel Cadmium Manganese Lead Zinc

(Ni) ppm (Cd) ppm (Mn) ppm (Pb) ppm (Zn) ppm
1 Gajanan Maharaj Chowk n.d. n.d. 0.07 0.45 2.19

2 Beed Bypass Road 0.30 n.d. 0.09 0.25 2.51
3 Waluj Industrial Area n.d. n.d. 0.19 0.93 2.37
4 City Chowk Police Station 0.30 n.d. 0.11 0.73 2.55
5 TV Center Chowk 0.21 n.d. 0.01 1.21 n.d.
6 Airport, Chikalthana n.d. n.d. 0.05 1.13 2.44
7 S. B. College, Aurangpura 0.75 0.01 0.10 0.61 2.28
8 Railway Station Chowk n.d. 0.01 0.13 0.57 2.38
9 Seven Hill, Aurangabad 1.02 n.d. 0.15 n.d. 2.48
10 Cidco Bus Stand, Aurangabad 2.09 n.d. n.d. 0.69 1.48
11 Gulmandi Chowk 0.21 0.01 0.07 1.42 2.42
12 Hotel Amarpreet Chowk 0.57 n.d. 0.15 0.85 2.33
13 Kranti Chowk 1.20 0.01 0.11 0.45 2.66
14 Mill Corner Police Headquarter n.d. n.d. 0.07 n.d. 1.35
15 MIDC, Chikalthana n.d. 0.01 0.09 n.d. 2.35
16 JNEC – West Wing 0.66 n.d. 0.07 n.d. 2.16
17 MGM Hospital Nursing College 0.11 n.d. 0.07 n.d. 2.34
18 Harshul T Point 0.84 n.d. 0.13 n.d. 2.22
19 MGM – Jr. College Clover
Dale School 0.57 n.d. n.d. n.d. 2.50
n.d. denotes not detected
3
2.5
Nickel (Ni) PPM
2 Cadmium (Cd) PPM

Manganese (Mn) PPM
1.5
Lead (Pb)
1 Zinc (Zn) PPM
0.5
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Cd was detected at SB College, Railway Station, Gulmandi Chowk, Kranti

Chowk, and MIDC Chikalthana. Vehicular emissions, automobile lubricants, wear
and tear of tires, and construction activities are the possible sources of Cd in ambient
air (Khillare and Sarkar 2012). Various products like batteries, toys, etc., contain
Cd. It is also more common in household garbage. In a previous study Cd was found
relatively enriched in Jharia street dust (Rout et al. 2012).
The mean quantity of Mn in PM10 of different selected sites was in order of Waluj
Industrial Area > Seven Hill > Railway Station >Harshul T Point. Mn is used in
unleaded gasoline to enhance octane rating and lessen engine knocking (Roy et al.
2012). Vehicular emission may account for the higher concentration of Mn in the study
area. Previous studies reported the earth crust/windblown soil as a contributor of Mn in
PM10 (Shah et al. 2006; Dubey et al. 2012). Coal also contains Mn in trace amount so
contribution of coal-burning activities and airborne coal dust cannot be neglected.
High concentrations of Lead (Pb) were detected in Gulmandi Chowk, TV center
Chowk, Airport, Waluj Industrial area, and Hotel Amarpreet Chowk. This is mainly
due to the heavy vehicular transportation. These values at the first three locations are
slightly higher than the Pb National Ambient Air Quality Standard (NAAQS)
(1.0 μg/m3) prescribed by the Central Pollution Control Board (CPCB) of India
(CPCB 2009). Lead is very toxic to human health as well as for the environment. Its
relatively high toxicity should represent a concern for the city.
High concentrations of Zn are observed at most of the locations monitored. Zn is
used in lubricating oil and Zn is also released from vehicular activities such as tire
wear (ATSDR 2005; TR MEF 2010).
Conclusion
The main aim of this research is to determine the levels of heavy metals including Pb,
Ni, Mn, Cd, and Zn in air samples collected from 19 different sites in Aurangabad city,
then compare the levels of heavy metals in the various sites, and deduce causes for the
presence of the heavy metals in air within the study area. Locations namely Kranti
Chowk, Railway Station, Waluj Industrial area, SB College, Gulmandi Chowk, and
Harshul T Point have revealed high concentrations of selected heavy metals mainly due
to resuspension of road dust by vehicular turbulence. Higher levels of air pollution on
account of growing number of automobiles, increase in the number of restaurants,
roadside eateries, and power generators have also been contributing factors. Waluj is an
industrial area and a cause of concern from declining air quality point of view. Waste
burning and construction activities across the city might have served as other sources.
To determine the sources of these metals, it is recommended to undertake more detailed
and comprehensive study.
Cross-References
Delhi City

Study of Delhi City
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Recent Advances in Membrane Extraction
Techniques for Environmental Samples 50
Analysis
Hadi Tabani, Saeed Nojavan, Kamal Khodaei, and Alireza Bazargan
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1210
Hollow Fiber Liquid-Phase Microextraction (HF-LPME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1211
Electromembrane Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1213
Emulsion Liquid Membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1217
Preparation of Emulsion Liquid Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1222
Applications of the Emulsion Liquid Membrane Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1223
Polymer Inclusion Membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1227
Applications of Polymer Inclusion Membrane Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1229
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1233
Abstract
The quantification of analytes present in environmental samples at trace levels
needs a preliminary stage of isolation and enrichment of compounds, and this
issue is a hot challenge in separation science. Usually, a direct analysis of
environmental samples to determine analytes is impossible. In recent years,
attempts have been made to develop new methodologies for the analysis of
environmental samples. Many methods have been developed for extracting
H. Tabani (*) · K. Khodaei

Department of Environmental Geology, Research Institute of Applied Sciences (ACECR), Shahid
Beheshti University, Tehran, Iran
e-mail: h_tabani@sbu.ac.ir
S. Nojavan
Department of Analytical Chemistry and Pollutants, Shahid Beheshti University, G. C., Evin,
Tehran, Iran
e-mail: s_nojavan@sbu.ac.ir
A. Bazargan (*)
Department of Civil Engineering, K. N. Toosi University of Technology, Tehran, Iran

https://doi.org/10.1007/978-3-319-73645-7_165
1210 H. Tabani et al.
different compounds from environmental samples. Among the emerging

techniques, membrane-based extraction is an efficient alternative to classical pre-
treatment methodologies. Membrane techniques have emerged as an efficient
method for the extraction of both ionizable and nonionizable analytes in complex
matrixes. The main advantages of these techniques include high selectivity, the use
of minimal organic solvents, and acceptable clean-up efficiency, with high enrich-
ment factors. Based on the recently published literature data, this chapter provides
an update of the advantages and applications of membrane extraction techniques
for analysis of environmental samples.
Keywords
Hollow Fiber Liquid-Phase Microextraction (HF-LPME) · Electromembrane ·
Polymer inclusion membrane · Emulsion liquid membrane
Introduction
Sample preparation has always been a somewhat neglected part of sample analysis. The
pretreatment allows for the migration of analytes from the primary matrix to the
receiving matrix with the simultaneous removal of macromolecules and other matrix
constituents that may interfere with the detection system. Frequently, liquid–liquid
extraction (LLE) is used as a conventional sample preparation method for extraction
of analytes from complex matrices (Carasek and Merib 2015; Płotka-Wasylka et al.
2016). The limitations of LLE techniques include long extraction times as well as the
use of large amounts of hazardous extraction solvents which are not environmentally
friendly. Also, often small enrichment factors and selectivity are achieved with LLE.
An alternative and complementary way for addressing this issue is applying membrane
technology. Membrane-based methods have brought about powerful options in sepa-
ration science, having some distinct advantages when compared to other classical
sample preparation methodologies. These methods have acceptable enrichment factors,
good cleanup efficiency, and selectivity while using only little or no organic solvents
(Jakubowska et al. 2005; Barri and Jonsson 2008). In membrane-based methods,
generally, a membrane (polymeric or liquid phase) is placed between two liquid phases
and acts as a selective barrier. One of these phases, the donor phase (DP), is containing
the analyte in a complex matrix. The analytes are then extracted to the other side of the
membrane which is called the acceptor phase (AP). Migration of analytes in the
membrane process results from the differences in the rate of mass transfer of analytes
across the membrane, and it depends on the type of the driving force (van Hout et al.
2003; Jonsson et al. 2003). The main driving forces are based on electric potential
difference (ΔE), concentration difference (ΔC), and pressure difference (ΔP).
Up to now, several kinds of membranes with different structures and transport
mechanisms have been introduced for extraction of analytes from environmental
samples. The distinction between membranes mainly originates from their diverse
preparation methods or raw materials. In this chapter, a comprehensive literature
study on the principles and applications of membrane extraction techniques based on
50 Recent Advances in Membrane Extraction Techniques for Environmental. . . 1211
liquid and polymeric membranes for analysis of analytes from environmental sam-
ples is discussed and outlined.
Hollow Fiber Liquid-Phase Microextraction (HF-LPME)
Generally, two extraction modes, namely two-phase extraction and three-phase extrac-
tion, are applied for HF-LPME (Amdany et al. 2015; Pedersen-Bjergaard and Ras-
mussen 1999; Vora-adisak and Varanusupakul 2006; Fakhari et al. 2013a). Two-phase
(aqueous-organic) LPME is used for extraction of analytes with high solubility in
organic solvents. In this mode, neutral compounds are extracted from the DP into the
membrane and subsequently into the organic solvent placed inside the hollow fiber as
the AP (Fakhari et al. 2013a; Li and Hu 2007; Varanusupakul et al. 2007; Chiang and
Huang 2007; Ma et al. 2011). The equipment used for the extraction is illustrated in
Fig. 1. In this method, the AP is in direct contact (as immobilized in the membrane
pores) with the aqueous sample: analyte molecules can diffuse directly into the
AP. After the extraction, the AP containing extracted organic phase is injected into
an analytical instrument for analysis. Conversely, in the three-phase (aqueous-organic-
aqueous) mode, the analytes migrate from the DP into an organic phase which is
immobilized inside the pores of the membrane, and then, they are extracted into
another liquid, the AP (Xia et al. 2007; Zhang et al. 2011; Li and Hu 2011; Payan
et al. 2011). Both two- and three-phase modes of HF-LPME have been applied for
extraction of analytes from environmental samples, and the present section focuses on
recent applications of the HF-LPME procedure in this area.
Fig. 1 Schematic illustration of the setup for EME. (Reproduced with permission from Elsevier
(Fakhari et al. 2013a))
One of the first publications which proposed using HF-LPME for analysis was by
Pedersen-Bjergaard and Rasmussen (Pedersen-Bjergaard and Rasmussen 1999). In
that work, three-phase LPME was used for preconcentration of methamphetamine
and subsequent analysis by capillary electrophoresis (CE). The study showed the
excellent potential of this technique for sample preparation. In the case where
the inner diameter of the hollow fiber does not tightly fit with the outer diameter
of the microsyringe needle, the hollow fiber might be separated from the
microsyringe needle during the extraction. In order to address this issue, Berhanu
et al. developed a new design for the quantification of three pesticides (fenthion,
chlorpyrifos, and diazinon) from environmental samples. In their method, after
impregnating the hollow fiber with n-undecane as the organic extraction solvent, it
was connected to a copper wire with appropriate outer diameter, in order to get it
tightly attached to the hollow fiber. This kind of configuration was found to be a
simple method with acceptable limit of detections (LODs) in the range of
15–80 ng L1 (Berhanu et al. 2008).
In an interesting study, Raharjo et al. used nylon instead of polypropylene as a
new support for determining quinalphos and methidation (Raharjo et al. 2009). In
another study, Nyoni et al. (2011) introduced a membrane which was made from
silicone rubber for quantification of ionizable organic compounds in environmental
samples. In this method, no organic solvents were used; hence, this method can be
classified as a green extraction technique. Also, the device was solid and it provided
stable and reputable results during the extraction with a longer lifetime compared to
conventional membranes. In addition, there have been some reports about using
polyvinylidene difluoride (de Jager and Andrews 2001), polysulfone (Vora-adisak
and Varanusupakul 2006), and cellulose (Zhang et al. 1996) as membranes for
HF-LPME.
Generally, when a pure solvent is used as the extraction solvent, analytes with log
P values lower than 2.0 are not efficiently extracted. It has been reported that
ion-pairing reagents such as tri-n-octylphosphine oxide (TOPO), tri-n- butyl phos-
phate (TBP), and di (2-ethylhexyl) phosphoric acid (DEHP) can alter the selectivity
of the HF-LPME method. For example, the addition of DEHP to membrane
improves the extraction of polar basic analytes with low log P values (log P < 1)
and, on the contrary, decreases the extractability of compounds with high log P
values (log P > 2). Trtić-Petrović proposed a method with mixing 10% of TOPO and
10% of TBP in n-hexyl ether to form the extraction solvent for the analysis of
16 pesticides from environmental samples (Trtić-Petrović et al. 2010). The results
showed that extraction efficiency of polar pesticides improved with the addition of
the mentioned reagents to the extraction solvent.
Also, the HF-LPME technique has been used for the quantification of metals in
environmental samples. Lopez-Garcia et al. determined trace concentrations of
mercury by adding a solution of 1-(2-pyridylazo)-2-naphthol (PAN) to the DP
(Lopez-Garcia et al. 2012). At first, a reversible complex formation between mercury
ions and PAN occurred and then diffused across the membrane to the AP. Peng et al.
reported application of ionic liquids as a new extraction solvent in HF-LPME. In this
study, 1-octyl-3- methylimidazolium hexafluorophosphate was reinforced within the
wall pores of the hollow fiber, and then chlorophenols were extracted from environ-
mental samples (Peng et al. 2007).
Further improvement in extraction efficiencies was achieved with the combina-
tion of solid-phase extraction (SPE) with LPME. Hu et al. (2009) introduced a novel
technique by adding molecular imprinted polymer (MIP) to the membrane for the
extraction of triazines from environmental samples. In this method, the mentioned
compounds were extracted by toluene as the organic phase in the membrane and
then adsorbed by the MIP. In another recent report, Yamini et al. (Moradi et al. 2012)
proposed an HF-LPME method for quantification of halogenated amines from
water samples. In this study, supramolecular solvents were used as extraction
solvents in the membrane, and the results showed that these kinds of solvents can
be good alternatives to conventional organic solvents. Recently, some scientific
reports on the automation of LPME instruments have been developed in the
literature (Maya et al. 2014; Vallecillos et al. 2012; Li et al. 2015). To conclude
this subject, Table 1 summarizes recent applications of HF-LPME in environmental
samples.
Electromembrane Extraction
Although the problem of organic solvent instability has been resolved by the
HF-LPME method, long extraction times are needed in order for the process to
achieve equilibrium (Pedersen-Bjergaard and Rasmussen 2006). In order to increase
flux of analytes across the membrane, transfer has also been carried out by application
of an electric field in a technique called electromembrane extraction (EME) (Fig. 2)
(Pedersen-Bjergaard and Rasmussen 2006; Fakhari et al. 2013b; Middelthon-Bruer
et al. 2008; Eibak et al. 2010; Koruni et al. 2014). The main mass transfer mechanism
for the migration of analytes across the membrane has been evaluated by the
Nernst–Planck equation (Middelthon-Bruer et al. 2008):

Di ν χ1
Ji ¼ 1þ ðCih Ci0 expðνÞÞ
h lnχ χ expðνÞ
where h is the thickness of the membrane, Di denotes the diffusion coefficient for the
analyte, Cih represents the analyte concentration at the membrane/DP interface, and
Ci0 is the analyte concentration at the AP/membrane interface; ν is a dimensionless
driving force defined as:
zi eΔ∅
ν¼
KT
where ΔØ is the electrical potential across the membrane, zi is the charge of the
analyte, e is the elementary charge, T is the absolute temperature, and K is
Boltzmann’s constant.
1214
Table 1 Different applications of HF-LPME in environmental samples

Detection
Target analytes Matrix Kind of membrane Extraction solvent system LOD (ppb) References
Organomercury Seafood, Polypropylene Toluene HPLC-UV 0.3–3.8 Xia et al. (2007)
environmental hollow fiber
samples
V (IV), V (V) Natural waters Polypropylene Carbon tetrachloride ETV-ICP- 0.086, 0.071 Li and Hu (2007)
hollow fiber OES
Haloacetic acids Aqueous samples Polypropylene 1-Octanol GC-ECD 0.1–18 Varanusupakul
hollow fiber et al. (2007)
Salicylates Aqueous samples Polypropylene 1-Octanol HPLC-UV 0.6–1.2 Zhang et al. (2011)
hollow fiber
Organometallic Aqueous samples, Polypropylene Tributyl phosphate CE-UV 0.68–6.90 Li and Hu (2011)
food hollow fiber
Haloethers Lake water Polypropylene Toluene GC-ECD 0.55–4.30 Chiang and Huang
hollow fiber (2007)
BTEX Water samples Polypropylene [BMIM][PF6] GC-FID 2.7–4.0 Ma et al. (2011)
hollow fiber
Sulfonamides Aqueous samples Polypropylene 1-Octanol HPLC-DAD 0.0003–0.033 Payan et al. (2011)
hollow fiber
Ni (II), Pb (II) Environmental Polypropylene [C6MIM][PF6] ET AAS 0.02 Abulhassani et al.
samples hollow fiber (2010)
Cr (III) Natural water samples Polypropylene [C4MIM][BF4] F AAS 0.7 Zeng et al. (2012)
hollow fiber
Hg (II) Aqueous samples Polypropylene Toluene ETAAS 0.06 Lopez-Garcia
H. Tabani et al.
50
Phenols Aqueous samples Polypropylene Dihexyl ether HPLC-DAD 0.14–0.29 Villar-Navarro

Endocrine disruptor Aqueous samples Polypropylene Dihexyl ether HPLC- 0.52–0.54 Villar-Navarro
hollow fiber fluorescence et al. (2013)
Estrogens Environmental Polypropylene Toluene:octanol HPLC-UV 0.055–1.46 Chen et al. (2013)
samples hollow fiber
Anti-inflammatory Aqueous samples Polypropylene 1-Octanol UPLC-MS/ 0.5–1.25 Zhang et al. (2013)
drugs hollow fiber MS
Pyrethroids Aqueous samples Polypropylene 1-Octanol GC–MS 0.002–0.012 San Román et al.
pesticides hollow fiber (2012)
Bisphenol A Aqueous samples Polypropylene 1-Octanol HPLC-DAD 0.2 Tan et al. (2012)
hollow fiber
Se (IV) Natural water Polypropylene 1-Octanol 0.02–0.1 Saleh et al. (2009)
hollow fiber
Hg (II) Fish, rice Polypropylene Propylbenzoate 0.012 Ensafi et al. (2012)
hollow fiber
Inorganic Sb Water Polypropylene 1-Octanol 1.1 Margui et al.
Tricyclic Water Polypropylene n-Dodecane 0.08–0.2 Ghambarian et al.
antidepressant drugs hollow fiber (2012)
Pesticides Industrial and fresh Polypropylene Toluene and ethyl acetate 3–350 Wang et al. (2012)
orange juice hollow fiber (85:15, v/v)
Atrazine Water, sludge water Polypropylene HPLC–UV 300 Hu et al. (2009)
hollow fiber
Recent Advances in Membrane Extraction Techniques for Environmental. . .
1215
Fig. 2 Schematic illustration of the setup for EME. (Reproduced with permission from Elsevier
(Fakhari et al. 2013b))
Generally, efficiency and the selectivity of the EME are controlled by the
chemical composition of the membrane and the type of organic extraction solvent.
Based on published papers, basic analytes with log P values approximately higher
than 2.0 have been extracted by nitro aromatic solvents such as 2-nitrophenyl octyl
ether (NPOE) (Eibak et al. 2010). When pure NPOE is used as the organic solvent,
basic analytes with polarities lower than 2.0 are not efficiently extracted. Addition of
only a low concentration of hydrophobic ion-pair reagents such as DEHP to pure
NPOE can promote the flux of basic compounds with low polarity and, on the
contrary, decreases the extractability of compounds with high log P values (Eibak
et al. 2010; Koruni et al. 2014).
Up to now, several modifications have been proposed to improve the mass
transfer of ionic analytes through the membrane. For example, crown ethers were
added to NPOE for the extraction of potassium ions. The results showed that NPOE
containing 1% w/v of dibenzo-18-crown-6 showed acceptable selectivity for extrac-
tion of K+ and had negligible recoveries for extraction of other cations (Slampova
et al. 2014). In another study, an ionic liquid ([C6MIm] [PF6]) as a new extraction
solvent was added in the membrane for the extraction of some basic drugs (Sun et al.
2014). Fakhari et al. proposed a new approach to improve the extraction of herbi-
cides such as 2,4-DB and Dicamba from environmental samples, where nonionic
surfactants were added into the sample to form a hydrophobic layer around the
herbicides, so that the mass transfer of analytes towards the membrane was promoted
(Bagheri et al. 2016).
Continuing with the improvement of this method, nanoparticles such as carbon
nanotubes (CNTs) (Hasheminasab et al. 2013), fullerene (Atarodi et al. 2017), and
N-doped graphene (ND-G) (Atarodi et al. 2016) were used to decorate the membrane
in order to improve of the mass transfer. The results showed EME recoveries were
increased in shorter time.
Another way for enhancing mass transfer could be obtained by decreasing the
boundary layer around the membrane. Seidi et al., by increasing the stirring rate and
decreasing the charge density around the membrane, reduced the thickness of the
double layer at the DP/membrane interface (Rouhollahi et al. 2016). In another
study, Tabani et al. reported a new method by using a rotating electrode for stirring
the AP (Asadi et al. 2016). With this new apparatus, extraction improved with
agitation of the AP due to decreasing thickness of the Nernst’s diffusion film around
the membrane/AP interface.
These days, the introduction of new kinds of membranes as alternatives to
polypropylene hollow fibers is a hot topic. Román-Hidalgo et al. (2017) introduced
a polar nano-structured (Tiss ®-OH) sheet containing high density of –OH groups for
the determination of highly polar analytes. Also, polyvinyldifluoride (PVDF) was
applied as a membrane material in a Parallel-EME (Pa-EME) method (Drouin et al.
2017). Most recently, some new membranes based on gels have been introduced by
Tabani et al. as green EME techniques (Tabani et al. 2017; Sedehi et al. 2018; Asadi
et al. 2018) (Fig. 3).
Another interesting development in EME is the use of microfluidic devices.
Microfluidic sample preparation techniques are very interesting, and the devel-
opment of these systems will surely flourish in the future. The first paper to
downscale the EME procedure was done by Petersen et al. (2010). After
that several papers were reported to miniaturize EME with on-chip dynamic-
EME and lab-on-chip systems (Drouin et al. 2016; Karami et al. 2017;
Abdossalami Asl et al. 2015). This design allows one to carry out analyses
with low amounts of DP and fast extraction because of a very short diffusion
path. Table 2 summarizes recent environmental applications of EME for extrac-
tion of analytes.
Emulsion Liquid Membrane
Owing to their high contact surface area for mass transfer, selective or accumula-
tive removal, and the need for low amounts of organic solvents, emulsion liquid
membrane (ELM) methods have been recognized as suitable methods for the
separation of pollutants from environmental samples. In the ELM process, the
stripping and extraction steps are combined into one step, leading to the simulta-
neous preconcentration of the target species (Cahn and Li 1974). There is also
significant saving on the amount of equipment and materials required in the
Fig. 3 Schematic illustration of preparation process of gel membrane. (Reproduced with permis-
sion from Elsevier (Tabani et al. 2017))
various stages of the liquid-liquid extraction. The ELM process includes three
steps and can be up to 40% more cost-effective than the solvent extraction process
(Frankenfeld et al. 1981). The first step involves preparation of an emulsion by
mixing the membrane phase and the internal phase, such as water in oil (W/O). The
second step is diffusion or transmission of dissolved species through the membrane
from the donor phase to an acceptor phase through surface contact between the
emulsion and the continuous phase. The third step involves emulsion and external
phases’ sedimentation due to emulsion breaking to recover the membrane phase.
Since the invention of the ELM method by Li in 1968 (Li 1968), application of this
method to hydrometallogically recover heavy metals has attracted the attention of
numerous researchers. The acceptor phase emulates an immiscible fluid mem-
brane. Then the emulsion is dispersed in the solvent or feed and the mass transfer
occurs from the feed to the internal acceptor phase. Liquid membranes could be
aqueous or organic solutions; however, studies have mainly addressed water-in-oil
emulsions. An experimental setup for the ELM technique is shown in Fig. 4 (Malik
et al. 2012).
Table 2 Overview applications of electromembrane techniques in environmental samples
50
Kind of Extraction Recovery LOD

Target analytes Matrix membrane solvent % Detection system (ppb) References
Pb (II) Amniotic fluid Polypropylene Toluene 81.6–86.3 CE-UV 20 Basheer et al.
4-Chlorophenol Seawater Polypropylene 1-octanol 74 HPLC-UV 0.1–0.4 Lee et al.
2,4- hollow fiber (2009)
Dichlorophenol
2,4,6-
Trichlorophenol
Pentachlorophenol
Amlodipine Water Polypropylene NPOE 83 CE-UV 3 Nojavan and
hollow fiber Fakhari (2010)
Li Standard Polypropylene 1-octanol 98 CE-C4D 0.063 Strieglerova
solution hollow fiber et al. (2011)
Salicylic acid Wastewater Polypropylene 1-octanol 66 HPLC-DAD 0.16 Payán et al.
Ketorolac hollow fiber 55 0.18 (2011)
Ketoprofen 62 0.12
Naproxen 58 0.08
Diclofenac 100 0.23
Ibuprofen 74 3.36
Chloroacetic acid Wastewater Polypropylene Toluene 87–106 HPLC-UV 0.0007 Alhooshani
Trifluoroacetic hollow fiber 0.0043 et al. (2011)
acid
Dichloroacetic 0.0193
acid
Phenyl acetic acid 0.0196
p-Hydroxyphenyl 0.0403
acetic acid
1219
(continued)
1220
Table 2 (continued)
Kind of Extraction Recovery LOD
Target analytes Matrix membrane solvent % Detection system (ppb) References
Trimipramine Water Polypropylene NPOE 66 CE-UV 7 Fakhari et al.
Salbutamol Wastewater Polypropylene NPOE +10% 53 HPLC-UV 10 Rezazadeh
Serbutaline hollow fiber DEHP +10% 43 5 et al. (2012)
TEHP
Ibuprofen Wastewater Polypropylene 1-octanol + CNTs 90 CE-UV 1.5 Hasheminasab
Naproxen hollow fiber 94 1 et al. (2013)
2,4-D Environmental Polypropylene 1-octanol 72 CE-UV 10 Tabani et al.
2,4-DB samples hollow fiber 71 10 (2013a)
Dicamba 70 15
Uranium Seawater Polypropylene NPOE +1% 54 Fluorescence 0.1 Davarani et al.
hollow fiber DEHP (2013)
2,4-D River water Polypropylene 1-octanol 40 CE-UV 0.3 Tabani et al.
2,4-DB hollow fiber 39 0.5 (2013b)
Dicamba 39 0.4
Cr (III) Environmental Polypropylene 1-octanol 31.1 HPLC-UV 5.4 Safari et al.
Cr (IV) samples hollow fiber 47.2 2.8 (2013)
Basic red-18 Wastewater Polypropylene NPOE 48 HPLC-UV 0.75 Nojavan et al.
Basic red-46 hollow fiber 81 0.30 (2013)
Basic red-51 78 0.30
Thorium Wastewater Culm 1-octanol +5% 93 UV- Vis 0.29 Khajeh et al.
DEHP (2015)
H. Tabani et al.
50
Fluoride Water samples Polypropylene 1-heptanol 49 IC 0.6 Nojavan et al.

Chloride hollow fiber 70 0.6 (2014)
Nitrate 46 1.5
Nitrite 47 1.5
Bromide 40 3.0
Phosphate 51 7.5
Sulfate 46 4.5
Ag (I) Wastewater Polypropylene 1-octanol +0.5% 67.6 Atomic absorption – Davarani et al.
Cd (II) hollow fiber DEHP+ 0.5% 81.4 spectroscopy – (2015)
Co (II) TEHP 63.3 –
Cu (II) 66.8 –
Zn (II) 86.5 –
Parabens Water samples Polypropylene 1-octanol 87–101 HPLC-DAD 0.98–1.43 Villar-Navarro
As(III) River water Polypropylene 1-octanol+2.5% 93–96 Anodic stripping 0.18 Kamyabi and
hollow fiber DEHP voltammetry (ASV) Aghaei (2016)
Pb (II) River water Polyvinylidene 1-octanol +20% 73.3–80 Square wave voltammetry – Hamsawahini
Sea water fluoride DEHP (SWV) et al. (2016)
Hg (II) River water Polypropylene 1-octanol +2% 86–93.8 UV- Vis 0.7 Fashi et al.
hollow fiber DEHP+ (2017)
Hg (II) River water Polypropylene 1-octanol +2% 41–43 Graphite furnace atomic 0.5 Kamyabi and
hollow fiber DEHP+ absorption spectrometry Aghaei (2017)
(GFAAS)
Au River water Polypropylene 1-octanol 95.6 UV- Vis 4.5 Khajeh et al.
1221
Fig. 4 Experimental setup for ELM technique. (Reproduced with permission from Elsevier (Malik
et al. 2012))
Preparation of Emulsion Liquid Membranes
Formulation is the main part in the liquid membrane process. This step involves
selection of a carrier, surfactant stripping agent, and diluents. Proper selection of
these components and their formulation will guarantee the success of extraction.
Various surfactants have been evaluated, yet only a few like Span 80 and ECA
4360 J have shown high efficiency (Ahmad et al. 2011). There is no specific
requirement for the selection of diluents; however, it is advantageous to have high
dissolution capacities for the extractor, high boiling temperature, and low solubility
in the feed and stripping phases, as well as being inexpensive and nontoxic. So far,
high speed lab-scale mixers or homogenizers have been used for emulsion
preparation.
Surfactants: Surfactants are amphipathic organic compounds, meaning that they
include both hydrophobic (their tail) and hydrophilic (their head) groups. Therefore,
they can dissolve in both organic and aqueous solvents. Surfactants reduce the
surface tension of liquids such as water. They are also known to decrease the
oil-water surface tension at the liquid-liquid interface.
Stripping agent: Acids or bases can be applied as a stripping phase in the ELM
process depending on the solute to be extracted. For example, Chiha et al. (2006)
used a NaOH solution as the internal phase for removal of chromium (VI) from
sulfuric acid aqueous solutions. Also, an H2SO4 solution has been applied for the
removal of Cr (VI) (Saravanan et al. 2006). The solute extraction speed improves
with an increase in the amount of stripping agent present in the emulsion.
Extractant: The extractant will be added to the membrane phase and serves as a
carrier. This carrier facilitates the transmission of target species through the mem-
brane. Carriers used in metals transport can include acidic carriers (-COOH, -SO3H,
or chelating groups) as well as basic carriers (such as N-H or ammonium salts).
Emulsion breaking: To break a W/O emulsion, electrostatic emulsion breaking
techniques are mainly employed (Lu et al. 1997). Other emulsion breaking tech-
niques are heating, phase dilution, and high stress (Devulapalli and Jones 1990).
Applications of the Emulsion Liquid Membrane Procedure
Metal Extraction
Removal of heavy and toxic metals is of crucial importance in environmental
protection. ELM technology has been proposed to improve extraction procedures
and reduce the consumption of solvents and carrier requirements in comparison with
other conventional solvent extraction techniques. Numerous reports have been pre-
sented in the field of ELM application for separation of metals such as gold, silver,
lanthanides, and rare earth elements. Table 3 provides several recent reports about the
application of ELM in inorganic pollutant separation. The selective extraction of
dysprosium by the ELM method has also been reported in which a new extractant
(Cyanex 572) was successfully used as a carrier (Raji et al. 2018). In another study,
more than 99% of Co and Ni were extracted from a chloride solution by use of Cyanex
301 (0.1 M) in a very short time (only 2 min) (Hachemaoui and Belhamel 2017). In
order to resolve the problem of cyanide wastewater, cyanide removal by use of a W/O
emulsion in the form of an emulsion liquid membrane was addressed by Xue et al.
(2016). Recovery of rare earth elements during wet processing of phosphoric acid
also has a great significance. When di(2-ethylhexyl) phosphate (D2EHPA) is used as
the carrier in the ELM method, high selectivity was seen, but a satisfying extraction
rate was not achieved. In this regard, Zhang et al. proposed a new ELM method in
which aniline was employed as a carrier for the extraction of rare earth elements from
the feed (Zhang et al. 2016). In another study, guanidine extractant (LIX 7950) was
proposed as a carrier in Cu and cyanide removal from cyanide-contaminated waste-
water (Lu et al. 2015). Bjorkegren et al. also introduced a new variation, through the
use of environmentally friendly and nontoxic diluent (like palm oil) for Cr
(VI) extraction from aqueous samples (Bjorkegren et al. 2015). Due to toxicity of
nanosilver ions toward aquatic organisms, release of nanosilver ions into the envi-
ronment has raised considerable concern. Logically, therefore, a study on using the
ELM method for the extraction of ionized nanosilver from washing water has been
conducted (Sulaiman et al. 2014). Mokhtari et al. used an emulsion membrane in
which calixarene nano-baskets were used as the carrier and surfactant for the extrac-
tion of alkali metals (Mokhtari and Pourabdollah 2013). More applications of the
ELM procedure can be found in Table 3 (Kassem et al. 2017; He et al. 2015; Elsayed
et al. 2013; Mousavi et al. 2012; Gupta et al. 2011).
1224
Table 3 Recent formulations of emulsion liquid membranes for extraction of metals and organic compounds
Stripping
Solute Matrix Extractant Surfactant agent Diluent References
Dysprosium Acidic solutions Cyanex 572 Span 80 HCl Kerosene Raji et al. (2018)
Cobalt, nickel Chloride solution Cyanex 301 Span 80 HCl Kerosene Hachemaoui and Belhamel
(2017)
Cyanide Wastewater TOA Span 80 NaOH Kerosene Xue et al. (2016)
Rare earth Phosphoric acid Aniline T154 HCl Sulfonated Zhang et al. (2016)
kerosene
Copper, cyanide Cyanide solutions LIX 7950 Span 80 KOH Kerosene Lu et al. (2015)
Cr (VI) Water TOMAC Tween 80 NaOH Palm oil Bjorkegren et al. (2015)
Nano-silver Wash water Cyanex 302 Span 80 Thiourea Kerosene Sulaiman et al. (2014)
Alkali metals Water Calixarene Calixarene (NH4)2CO3 Kerosene Mokhtari and Pourabdollah
(2013)
Paladium Nitrate medium Cyanex Span 80 KSCN Chloroform Kassem et al. (2017)
471X
Ce (IV) Sulfuric acid solution D2EHPA Span 80 HCl/H2O2 Sulfonated He et al. (2015)
kerosene
Uranium Phosphoric acid D2EHPA/ Span 80 TDDA Kerosene Elsayed et al. (2013)
TOPO
Arsenic (V) Water Cyanex 921 Span 80 Na2SO4 Kerosene Mousavi et al. (2012)
Mercury(II) Aqueous solutions D2EHPA Span 80 Thiourea Toluene Gupta et al. (2011)
H. Tabani et al.
50
Ethyl paraben Aqueous solution TOA Span 80 Na2CO3 n-Heptane Kohli et al. (2018)
Diclofenac Wastewater TBAB Span 80 NaOH Dichloromethane Seifollahi and Rahbar-
Kelishami (2017)
Lignin Pulping wastewater Aliquat 336 Span 80 NaHCO3 Kerosene Ooi et al. (2016)
Phenylalanine Sodium chloride D2EHPA Span 80 HCl Kerosene Fang et al. (2016)
solutions
Anabasine Alangium Acetic acid Butadiene styrene H2SO4 Kerosene Guo et al. (2015)
platanifolium root rubber
Acetaminophen Water Aliquat Span 80 KCl n-Hexane Chaouchi and Hamdaoui
336 (2014a)
Rhodamine 6G Wastewater D2EHPA Span 80 H2SO4 Kerosene Othman et al. (2013)
4-Chlorophenol Water – LK-80 NaOH Kerosene Kargari (2013)
Propylparaben Aqueous solution TOPO Span 80 Na2CO3 n-Hexane Chaouchi and Hamdaoui
(2015)
4-Nitrophenol Water – Span 80 Na2CO3 n-Hexane Chaouchi and Hamdaoui
(2014b)
Crystal violet, Water – Span 80 NaOH Oil Agarwal et al. (2010)
methylene blue
Congo red Aqueous solution – Span 80 Na2CO3 n-Hexane DAas and Hamdaoui (2010)
Gibberellic acid Fermentation Aliquat Span 80 KCl n-Heptane Berrios et al. (2010)
broths 336
1225
Extraction of Organic Compounds

Although the emulsion membrane method has been mostly used to remove and
extract metals, application of this method in organic compound removal has also
been investigated, and there exist several reports in this area. Recently, the ELM
method was used for ethyl paraben (EP) removal from aqueous solution; this
method involved the use of trioctylamine (TOA), n-heptanes, Span 80, and
Na2CO3 as the carrier, diluent, surfactant, and stripping agent, respectively
(Kohli et al. 2018). Through the use of a sustainable emulsion in optimal condi-
tions, almost 90% of the EP could be recovered (Kohli et al. 2018). ELM can also
be employed for treatment of pharmaceutical wastewater due to its high extraction
efficiency in a short time. In this context, Diclofenac was separated from waste-
water samples using the ELM method (Seifollahi and Rahbar-Kelishami 2017).
Under optimal conditions, the maximum extraction from DCF was 99.65%. In
another study, up to 95% of lignin was extracted from pastry wastewater (Ooi et al.
2016). Hence, ELM is an alternative technology for the separation of some organic
materials from their solutions. Recently, phenylalanine was extracted from sodium
chloride solutions using the ELM method as a selected model system in which
sulfonated kerosene was used as a diluent (Fang et al. 2016). The flow chart of this
extraction process is shown in Fig. 5. An experimental study was also conducted
on the extraction of DL-anabasine from Alangium platanifolium root (APR) using
the ELM system (Guo et al. 2015). In this study, an emulsion liquid membrane was
prepared using an emulsifier (styrene-butadiene emulsifier) as an alternative to
Span 80, and acetic acid and kerosene were applied as carriers and diluents,
respectively. The results indicated that the extracted DL-anabasine was three
times greater than that extracted by liquid-liquid extraction. Acetaminophen
extraction from aqueous solution with the ELM method in which Aliquat
336 was employed as a carrier has also been reported (Chaouchi and Hamdaoui
2014a). Under favorable conditions, the practical extraction of all acetaminophen
molecules from the external feed solution was shown to be possible. In another
study, the extraction of rhodamine 6G (R6G) from liquid wastewater was
addressed (Othman et al. 2013). Chlorophenols (CP) are hazardous compounds
Internal Membrane
Phase Phase External Phase
Extract Membrane
Phase
Raffinate Concentrate
Emulsion Extraction Stratification Demulsification
Fig. 5 Flow chart for the extraction process of l-phenylalanine by ELM. (Reproduced with
permission from Elsevier (Fang et al. 2016))
produced during chlorination of phenol in water purification systems. These

materials are considered as harmful substances in wastewater and exhibit toxicity
even at very low concentrations. Therefore, recovery and recycling methods for
treatment of CP-containing wastewater (rather than destructive methods such as
chemical oxidation and garbage incineration) should be developed. In a recent
study, 4-CP extraction from aqueous solutions was investigated (Kargari 2013).
More applications of the ELM method for the extraction of organic compounds can
be found in Table 3 (Chaouchi and Hamdaoui 2014b, 2015; Agarwal et al. 2010;
DAas and Hamdaoui 2010; Berrios et al. 2010).
Polymer Inclusion Membrane
The concept of polymer-based liquid membrane emerged about 50 years ago, but
such membranes have been recently named polymer inclusion membranes (PIMs)
(Nghiem et al. 2006). As PIM-based separation is a better alternative to solvent
extraction, the popularity of these materials is exponentially increasing (Almeida
et al. 2012). PIMs are a kind of liquid membrane consisting of a liquid phase and
a base polymer. The base polymer (e.g., cellulose tri-acetate (CTA)) which is
usually selected based on the extractant or specific application (Pereira et al.
2009) forms the membrane skeleton and provides mechanical strength. The liquid
phase contains a carrier or extractant which is responsible for extracting the
species through formation of an ion pair. PIMs are usually prepared by dissolving
all components of the membrane in a small volume of a volatile solvent (e.g.,
Tetrahydrofuran) and pouring the solution on a special surface depending on the
application. PIMs can be customized not only physically, but also chemically,
since the chemical composition of the membrane can be well prepared for a
particular analyte through selecting the proper extractants, plasticizers, modifiers,
and polymers (Pereira et al. 2009). Similar to the other liquid membranes
(supporting liquid membrane (SLMs)) (Chaouchi and Hamdaoui 2015), PIMs
allow for simultaneous extraction and back-extraction on both sides of the
membrane and facilitate the selective transfer of the target analyte along the
membrane (i.e., from the donor to acceptor solution); therefore, the species
would be extracted or preconcentrated. As no volatile and toxic organic solvents
are used in this process, these membranes are environmentally friendly and hence
separations with use of expensive reagents can be justified. In contrast to SLMs,
in which the liquid phase is protected within pores of membranes, PIMs incor-
porate the membrane liquid phase in the composite chains of the base polymer,
thus reducing its tendency to leach adjacent aquatic phases. Therefore, PIMs are
substantially more stable and stronger than SLMs (Almeida et al. 2012). All these
PIM advantages have attracted a lot of attention in chemical analysis as they can
be helpful in improving the sensitivity and selectivity. Figure 6 shows how PIMs
can be applied in each of these analytical operations (Almeida et al. 2017).
Hence, recent applications of this method in purification of metals and organic
pollutants will be discussed in the continuing sections.
1228
SENSING SAMPLE PRE-TREATMENT PASSIVE SAMPLING

ISE Optode Separation
Transport cell
Potentiometer Light detector
Sample Receiving Receiving
solution solution solution
Optical fibre
PIM
Pre-concentration
Flow-through approach PIM
Optical fibre
Sample solution
Flow Flow PIM Sample solution

in out Receiving solution (e.g. creek)
ISE body
Reference electrode
Hollow PIM
Sample
PIM
solution
solution
Receiving
Sample
Sample solution solution
Fig. 6 General schematic representation of PIM applications in chemical analysis. (Reproduced with permission from Elsevier (Almeida et al. 2017))
H. Tabani et al.
Applications of Polymer Inclusion Membrane Procedure
Metal Extraction
PIMs have been used for extraction of various metals from different and compli-
cated solutions. Recently, a study addressed the use of a PIM based on poly
(vinylidene fluoride-co-hexa-fluoropropylene) in which Cyphos ® IL 101 (trihexyl
(tetradecyl) phosphonium chloride) was used as carrier and NPOE was employed as
plasticizing agent (in weight ratio of 55/35/10) for online extraction of Vanadium
(V) (Yaftian et al. 2018a). In this study, xylenol orange was employed as a
colorimetric reagent. It should be noted that the morphology and mechanical
properties of the PIM could also affect the extraction procedure. This was first
investigated by Witt et al. for the extraction of Zn ions from aqueous solutions (Witt
et al. 2018). The possibility of selective separation of lanthanide ions from sulfuric
acid solutions was first investigated through use of a PIM including 45%
wt. D2EHPA and 55% wt. PVC (Croft et al. 2018). It was revealed that complete
back-extraction of the same ions from PIM is achievable by sulfuric acid-containing
solution in concentrations of 7.0, 1.0, and 0.3 M. In a review article, the increasing
interest in PIMs was highlighted in analytical chemistry (Almeida et al. 2017). This
review article presented an overall view about the analytical chemistry application
of PIMs and revealed their adaptability for resolving challenging chemical analysis
problems. Finding new carriers is an interesting field in PIM applications. A study
has also comprehensively described the relationship between transport perfor-
mance of Cr(VI) through ionic PIMs based on PVDF-co-HP (IPIM) and the length
of alkyl chain of ionic liquids based on symmetrical imidazolium bromide at room
temperature as a new carrier (Turgut et al. 2017). Aza [18]crown-6 and β-diketone
derivatives are also among the other new carriers which have been employed for
extraction of silver and zinc ions, respectively (Kolodziejska et al. 2017; Witt et al. 2016).
Nowadays, graphene oxide plays a crucial role in extraction techniques. In a
unique study, Cr(VI) removal by graphene oxide-based PIMs from Cr plating
water was investigated (Kaya et al. 2016). A new approach has been created for
determination of Al3+ in aqueous samples through use of optode membrane
produced by the addition of aluminum-selecting reactants to PVC (Suah et al.
2015). Addition of Triton X-100 in the membrane phase is useful in improving Al3
+
ions absorption from the liquid phase. Therefore, it can increase the absorption
intensity of optode (Suah et al. 2015). Moreover, a paper-based sensor was
proposed on the basis of PIMs which can be used for the determination of Cu
(II) in water (Jayawardane et al. 2013). In this device, PIM contained PVC, di
(2-ethylhexyl) phosphoric acid, dioctyl phthalate, and PAN, and the intensity of
Pan-Cu2+ complex color was determined by a flatbed scanner. Passive diffusion is
the major driving force in PIM-based extraction. However, there are some reports
on the application of an electric field in PIMs, to improve extraction kinetics
(Chaudhury et al. 2016; Mamat and See 2015; Schmidt-Marzinkowski et al.
2013; See et al. 2013; See and Hauser 2011). For example, the applicability of
cellulose acetate membranes for the extraction of inorganic anions by an electric
field has been investigated. Extraction of highly lipophilic ions (such as perchlo-
rate) is also possible with membranes without the use of any ionic carrier. How-
ever, ions with lower lipophilic properties need a carrier (Schmidt-Marzinkowski
et al. 2013). Many PIM applications can be found in Table 4 (Yaftian et al. 2018b;
Arslan et al. 2017; Kagaya et al. 2017; Baczynska et al. 2016; Gaytan et al. 2014;
Zawierucha et al. 2013).
Organic Compound Extraction

PIMs have been usually employed for the removal or preconcentration of inorganic
compounds. However, there are some particular reports about the use of PIMs for
organic compound extraction. Malachite green is an organic compound which has
been controversially used as a dye for coloring hair and as an antimicrobial agent in
aquaculture as well. In a recent study, this compound was extracted from real and
synthetic wastewater solutions with a PIM (Ling and Suah 2017). The PIM
contained poly(vinyl)chloride (PVC) as a polymer, bis-(2-ethylhexyl) phosphate
(B2EHP) as the extractant and dioctyl phthalate (DOP) as a plasticizing agent (Ling
and Suah 2017). After optimizing the PIM composition, the average extraction
efficiency was more than 98%. In a similar study, some acid dyes were extracted
from environmental samples by PIMs consisting of cellulose triacetate as the base
polymer, NPOE as plasticizer, and tricaprylmethylammonium chloride (Aliquat
336) as carrier (Salima et al. 2016). As a highly consumed antibiotic, sulfamethox-
azole (SMX) has been commonly found in wastewater treatment plants and periph-
eral waters. It has adverse effects on living organisms and therefore needs to be
removed from aqueous systems. A study focused on the development of PIM-based
passive samplers containing Aliquat 336 as an extractant and carrier for tracking
SMX in aqueous systems (Rodriguez et al. 2016). Also, other antibiotics have been
extracted from wastewater samples based on PIMs (Rodriguez et al. 2015; Perez-
Silva et al. 2012).
PIMs have several important properties. They are nonporous membranes and dry
substances which can be prepared prior to application and stored without significant
deterioration for extraction operations. In a study, an in-line coupling of the
PIM-based microextraction method was shown for the first time with a separation
method for clinical purposes, and formate (the main metabolite in methanol toxicity)
was determined in undiluted human plasma and whole blood by capillary zone
electrophoresis (CZE) (Pantuckova et al. 2015). Transport of organic acids, such
as oxalic acid and lactic acid, was carried out through a PIM. As a polymer, cellulose
tri-acetate (CTA) was used and 1-alkylimidazole (IMI-n, n = 10, 11, 12, 14) was
employed as the carrier (Przewozna et al. 2014). As a pollutant, phenol can also be
removed from water samples by the PIM method. The first study on the application
of a PIM for phenol removal and transfer from aqueous solutions and contaminated
water was reported by Perez-Silva et al. (2013). The results indicated that this
process was highly discriminative for phenol even in heavily polluted waters.
Other applications of PIMs for the extraction of organic compounds can be found
in Table 4.
Table 4 Recent formulations of polymer inclusion membranes for extraction of metals and organic compounds
50
Analyte Matrix Polymer Carrier Plasticizer References

V(V) Dietary PVDF- Cyphos® IL 101 NPOE Yaftian et al. (2018a)
supplements HFP
Zn(II) Water PVC ACAC/D2EHPA DAO Witt et al. (2018)
La(III), Ga(III), H2SO4 PVC D2EHPA – Croft et al. (2018)
Yb(III)
Cr(VI) Water PVDF- RTILs TEHP Turgut et al. (2017)
HFP
Ag (I), Cu(II) Wastewater CTA N-(diethylthiophosphoryl)-aza[18]crown-6/ NPOE Kolodziejska et al.
N-(diethyloxophosphoryl)-aza (Payan et al. 2011) crown-6 (2017)
Zn(II) Water PVC β-Diketone derivatives ADO Witt et al. (2016)
Cr(VI) Chrome plating CTA Calix [4]arene derivative NPOE Kaya et al. (2016)
water
Al3+ Water PVC Triton X-100 DOP Suah et al. (2015)
Cu(II) Wastewaters PVC D2EHPA DOP Jayawardane et al.
(2013)
Inorganic anions Water CTA Aliquat 336 NPOE Schmidt-
Marzinkowski et al.
(2013)
V(V) Sulfate solutions PVDF- Cyphos® IL 101 NPOE See and Hauser (2011)
HFP
Zn(II) Water CTA NaDDTC NPOE Arslan et al. (2017)
Cr(VI) Acidic solution PVC Aliquat 336 – Kagaya et al. (2017)
Zn(II), Fe(II), Fe Chloride CTA Cyphos® IL 101 NPOE Baczynska et al. (2016)
(III) solutions
Au(III) HCl media CTA – NPOE Gaytan et al. (2014)
Pb(II), Cd(II), Zn Landfill leachate CTA Resorcinarene NPOE Zawierucha et al.
(II) (2013)
1231
(continued)
1232
Table 4 (continued)
Analyte Matrix Polymer Carrier Plasticizer References
Malachite Green Wastewater PVC B2EHP DOP Ling and Suah (2017)
Acid dye Aqueous CTA Aliquat 336 NPOE Salima et al. (2016)
solution
Sulfamethoxazole Aquatic systems CTA Aliquat 336 NPOE Rodriguez et al. (2016)
Formate Human serum/ CTA Aliquat 336 NPOE Rodriguez et al. (2015)
whole blood
Organic acids Water CTA 1-Alkiloimidazole – Przewozna et al. (2014)
Phenol Polluted water CTA Cyanex 923 NPOE Perez-Silva et al.
(2013)
Phenol Aqueous PVC N503 N503 Meng et al. (2015)
solution
Citric acid Water CTA 1-Alkylimidazoles – Gajewski et al. (2014)
H. Tabani et al.
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Environmental Toxicology and
Air Pollution: A Comparative Analysis 51
of Different Methods and Studies
Gustavo Marques da Costa, Larissa Meincke, Darlan Daniel Alves,

Ane Katiussa Siqueira Frohlich, Sandra Manoela Dias Macedo, and
Daniela Montanari Migliavacca Osório
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1244
Environmental Health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1246
Air Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1247
Impacts of Air Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1250
Environmental Monitoring: Air Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1257
Methodologies Related to Environmental Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1258
Active and Passive Biomonitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1258
Comparative Analysis of Different Studies and Parameters:
Environmental Toxicology and Atmospheric Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1260
Final Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1263
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1263
G. M. da Costa (*)
Programa de Pós-graduação em Qualidade Ambiental, Universidade Feevale,
Novo Hamburgo, RS, Brazil
L. Meincke
e-mail: larissa_meincke@yahoo.com.br
D. D. Alves · D. M. M. Osório
Programa de Pós-graduação em Qualidade Ambiental, Universidade Feevale,
Novo Hamburgo, RS, Brazil
e-mail: darlandaniel@gmail.com; danielaosorio@feevale.br
A. K. S. Frohlich
UFMG, Belo Horizonte, Brazil
e-mail: anebiomed@yahoo.com.br
S. M. D. Macedo
Departamento de Farmacociências, UFCSPA, Porto Alegre, Brazil
e-mail: sandramd@ufcspa.edu.br; smdmacedo@icloud.com

https://doi.org/10.1007/978-3-319-73645-7_170
Abstract
The degradation of air quality is increasing in several regions of the world, making
air improper or harmful to human health and the environment. The environmental
toxicology aims to establish the safety limits of a chemical agent and assessment of
environmental exposure, anticipating the consequences of damage to human
health. The objective of this chapter will be to present concepts and methods
related to environmental toxicology and atmospheric pollution, as well as a
mapping of parameters and studies carried out involving the theme in question.
In the atmosphere, the effects of pollutants include, in addition to damage to
vegetation, soil, and materials, the increase of particles, thus reducing visibility
and inhibiting solar radiation received; the increase of the concentrations of
gaseous pollutants that absorb longwave radiation and increase the surface tem-
peratures; and also the alteration of precipitation, reducing the amount of rain due
to the increase of particles that function as a cloud condensation nucleus. In human
health, exposure to air pollutants can affect the respiratory system, cardiovascular
system, and nervous system, leading to increased mortality and morbidity. The
importance of the use of environmental parameters is associated with its use as
an instrument for planning and managing urban spaces, serving to make better use
of natural resources and also as a preventive measure against environmental
degradation.
Keywords
Air quality · Human health and the environment · Pollutants · Urban spaces
Introduction
The degradation of air quality is increasing in several regions of the world, making
air improper or harmful to human health and the environment. Changes in air quality
are more relevant in large urban centers or impact areas of industrial activities of high
polluting potential, such as in the areas of mining and thermoelectric processes. In
addition to industrial activities, vehicle emissions represent a significant percentage
of the degradation of air quality in several regions. In this context, vehicle traffic can
account for more than 50% of particulate emissions emitted into the atmosphere.
The World Health Organization (WHO 2013) recommends that current limits on the
emission of pollutants should be revised because even under current legislation, studies
indicate that concentrations affect human health. Currently, air pollution can be con-
sidered as the major environmental risk factor and greatly responsible for affecting
human health, leading to increased mortality and morbidity. The WHO warns that more
than 90% of the world population breathes contaminated air. Epidemiological evidence
about the health effects of air pollution is growing and evolving rapidly. Air pollution
was responsible for the deaths of 7 million people worldwide and 14,100 new cancers
in 2012, doubling compared to the previous 4 years (WHO 2014). Of the approxi-
mately 3 million deaths that occur annually as a result of air pollution, 94% occur as a
51 Environmental Toxicology and Air Pollution: A Comparative Analysis of. . . 1245
result of noncommunicable diseases – mainly cardiovascular diseases, strokes, chronic

obstructive pulmonary diseases, and lung cancers – besides also increasing the risk of
acute respiratory infections (WHO 2016). The regions of the low- and middle-income
are the main affected ones, reflecting 97% of these cities that do not comply with WHO
guidelines. The serious environmental problem is reiterated by the study conducted in
the last 2 years, and in 103 countries, covering more than 3000 cities, air pollution
levels doubled (WHO 2016).
The growing environmental and public health concern related to the particulate
matter, particularly inhalable particulate matter, is associated with damage to human
health, as it has been classified by the International Agency for Research on Cancer
as a human carcinogen (Group I) (Bocchi et al. 2016). Thus, the concern to evaluate
the chemical composition of the particulate material, mainly the inhalable particles
with the particle size of less than 10 μm, is associated with an important adsorption
characteristic of chemical substances on its surface and that can be transported to
the lower respiratory tract, the alveoli. These particles can also affect climate and
vegetation and reduce visibility (Basha et al. 2010). The toxicity of these particles
is not only associated with the increase in mass but also its chemical composition
and shape (Moreno et al. 2006). The atmospheric particles comprise a complex
mixture of various elements and chemical compounds such as sulfates, nitrates,
ammonia, organic compounds (PAHs, nPAHs, and others), marine salts (NaCl),
soil elements (Al, Si, Ti, Ca, Fe), and metallic elements (Pb, Zn, Ni, Cu, V, Cr,
Cd, and Hg, among others).
Exposure to air pollutants can have severe consequences on the metabolism of
individuals and their populations, ultimately leading to loss of viability. Considering
that atmospheric contaminants tend to be precipitated by the rains, and through their
percolation, they present themselves as a potential source of diffuse pollution.
Therefore, the assessment of the environmental risks associated with its launch is
essential, and the toxicity bioassays constitute an important tool for environmental
monitoring, allowing the evaluation of complex mixtures to which the populations
may be exposed (Alves et al. 2016). Bocchi et al. (2016) evaluated mutagenicity
(Salmonella test) and genotoxicity (comet and micronucleus test in cell line A549)
in the fine particulate matter (MP2.5 and MP1.0), also quantifying HPAs. The results
showed a greater presence of mutagenicity in samples of particulate matter
collected in winter and fall. However, the results with the comet test did not present
seasonality. Thus, the use of different mutagenicity and genotoxicity assays applied
to the particulate matter proved to be relevant. Palacio et al. (2016) evaluated the
soluble fraction of total suspended particles and particulate matter (MP10 μm)
in different samples collected in the state of São Paulo, Brazil. The results of the
mutagenicity tests using the Salmonella assay showed positive results for all the
samples evaluated.
In this context, the objective of this chapter will be to present concepts and
methods related to environmental toxicology and atmospheric pollution, as well as
a mapping of parameters and studies carried out involving the theme in question. The
presented methods can be applied to the elaboration of environmental diagnoses in
regions with different magnitudes of environmental impacts.
Environmental Health
Environmental health is conceptualized as the relationship between the environ-

ment and the health standard of a population. This relationship incorporates all the
elements and factors that potentially affect health. Thus, new theoretical
approaches to the relation production/environment/health are studied, aiming at
finding explanations about how this relationship occurs, pointing out and propos-
ing interventions based on preventive actions to reduce risk, and having as a risk
the likelihood of an adverse effect occurring during a given exposure time. While
environmental toxicology aims to establish the safety limits of a chemical agent
and assessment of environmental exposure, anticipating the consequences of
damage to human health (Brilhante and Caldas 1999), the potential risk in envi-
ronmental toxicology deals with the study of the likelihood of sources harmful to
health and the environment, capable of causing damage, disease, or death to living
beings when in concentrations higher than those they can assimilate under normal
conditions, that is, to absorb, to distribute, to metabolize, and to eliminate the
organism. Therefore, it is defined as:
• Risk: the measured or estimated probability of damage, illness, or death caused by

a chemical agent in an individual exposed to it.
• Danger: qualitative term that expresses the agent’s harmful potential for health
and/or the environment.
• Risk assessment: the first step in triggering decision-making processes comes
from knowing the cause-effect relationship and possible damages caused by
exposure to a particular chemical agent. The stages of risk assessment are:
– Danger identification: this is the identification of the dangerous agent in its
essence, its effects, the exposure conditions, and the target population.
– Exposure assessment: refers to the quantification of the concentration of the
harmful agent in an environment, for an individual or group.
– Risk estimation: relates the quantification of the dose-response or dose-effect
relationship to a given environmental agent, demonstrating the likelihood and
nature of its effects on health and the environment.
– Exposure or dose: it is the quantitative definition of the concentration of
chemistry that reached (external dose) the individual or that which was
absorbed (internal dose) by him.
– Risk characterization: this is the meeting of the previous stages that, in
possession of all available data on the subject, characterizes the specific use
or occurrence of damage, illness, or death caused by exposure to a particular
concentration of a chemical agent.
– Management or risk management: thus conceived, it refers to the comparison
of calculated risk or public health impacts, environmental exposure to the
agent, as well as the possible contribution of social and economic factors
that also include the benefits associated with these factors. Ultimately, in this
process, it can be established that under the proposed conditions, the risk may
be acceptable (Brilhante and Caldas 1999; Amaral e Silva 2004).
Air Pollutants
The rapid growth of the population, as well as the processes of industrialization

and urbanization associated with the high consumption of energy and the delay in
measures to control atmospheric emissions, especially in emerging countries, has led
to an increase in pollutant emissions and, consequently, serious problems of air
pollution (Migliavacca et al. 2012; Rodriguez et al. 2015).
The main anthropogenic sources of air pollutants are industries (production
of both raw materials and other products), automotive vehicles (gasoline, diesel,
alcohol), thermoelectric plants, biomass, and fossil fuel burning. These emitting
sources may be classified, by their nature, into mobile and fixed sources. Mobile
sources are those that are not located in a fixed place, being able to move (automo-
biles), and fixed sources are located in a specific, fixed point (chimney).
Air pollutants can be classified according to their origin (primary and secondary),
composition (organic and inorganic), and physical state (particulate matter,
gases/vapors). Primary pollutants are those emitted directly by sources of emission
into the environment, for example, sulfur dioxide, nitrogen oxides, carbon monox-
ide, volatile organic compounds, and particulates. Secondary pollutants are those
formed by chemical reactions (hydrolysis, oxidation, or photochemical reactions).
Among the primary pollutants and natural components present in the lower atmo-
sphere and fractions of solar radiation, for example, emitted sulfur dioxide reacts
with oxygen from the air to form sulfur trioxide, which reacts with water vapor to
form sulfuric acid, one of the components of acid precipitation. The sources of
air pollutants can be originated through natural or anthropogenic events. Natural
sources can be volcanic eruptions with the emission of ashes and gases, decompo-
sition of animals and plants, resuspension of soil dust by the winds, formation of
methane gas in swamps, marine aerosols, plant pollen, and natural forest fires,
among others.
Air pollution can be classified into levels: local, urban, regional, transboundary,
and global. At a local level (5 km radius), pollution is characterized by high
concentrations of specific pollutants that may originate from automobiles or indus-
trial activities in that region. The lower the launch height of a source, the greater the
potential impact for a given release. At the urban level, three main types of pollution
are characterized: high average of annual concentrations of various pollutants (from
industrial and automobile activities); winter-type smog, when low temperatures and
mists in the year are observed (from industries); and summer smog, or photochem-
ical smog (from motor vehicles), favored by sunlight and high temperatures.
However, regional air pollution (50–1000 km) can be attributed to the transport
and dispersion of urban pollutants in large areas and the transport and transformation
of primary pollutants to secondary levels at a regional level. Associated with these
mechanisms are problems such as the formation of tropospheric ozone and acid rain.
Transboundary air pollution is related to the transfer of air pollution from one
country to another, and problems that occur at a regional level may also occur
between adjacent countries. Global pollution is related to two known problems
which are the greenhouse effect and the decrease of stratospheric ozone. It is derived
from anthropogenic actions contributing to the other levels mentioned above,

and the accumulation of pollution from these levels can contribute to the increase
of pollution at the global level. Thus, high concentrations of toxic gases and other
pollutants emitted into the atmosphere, mainly through anthropogenic sources, have
been responsible for causing adverse effects on human health, climate, and
the environment (Seinfeld and Pandis 2006; Li and Zhang 2014). Recent greenhouse
effect gas emissions are the largest in history, making them the main causes of global
warming. In addition, since each part of the planet is interconnected through
atmospheric transport, emissions from one continent can reach the other, causing
impact on the climate on a global scale and not just locally (Seinfeld and
Pandis 2006).
In order to understand the harmful effects of atmospheric pollutants on humans
and the environment, its constituent is studied, the particulate matter (PM), which is
composed of a set of adsorbed pollutants composed of dust, smoke, and all kinds of
solid and liquid material that remain suspended in the atmosphere because of its
small size. Particulate matter may be classified as:
(a) Total suspended particles (PTS), which can be defined in a simplified manner as
those whose aerodynamic diameter is less than 50 μm. Some of these particles
are inhaled and can cause health problems and can adversely affect the quality of
life of the population, interfering with environmental conditions and harming
normal community activities.
(b) Inhalable particles (MP10) are those whose aerodynamic diameter is less than
10 μm. Inhalable particles can also be classified as fine inhalable particles –
MP2.5 (<2.5 μm) – and coarse inhalable particles (2.5–10 μm). The fine parti-
cles, due to their small size, can reach the pulmonary alveoli, whereas the coarse
particles are retained in the upper part of the respiratory system (Salgado 2002).
Concerning environmental exposure, most situations involve exposures to

low concentrations of atmospheric pollutants for a long time, resulting in
increased risk and damage to health, which may arise after a long period, thus
making it difficult the establishment of the causal nexus. However, it is
necessary to consider that the harmful action of the pollutants depends on the
possible interactions that can occur of a combined exposure and the inter-
ference of other organic compounds present in the respirable material (Cimino
et al. 2014).
Polycyclic aromatic hydrocarbons (PAHs) are organic compounds consisting
of two or more condensed benzene rings, usually occurring in complex mixtures
that comprise hundreds of compounds and are often associated with particulate
matter. PAHs have characteristics such as low solubility in water, low vapor pres-
sure, and high melting and boiling points. At ambient temperature, they appear as
solids, ranging from semi-volatile molecules to molecules with high boiling points.
Their concentrations can range from a few ng m3 to 100 ng m3. The composition
profiles of these mixtures vary according to the generation process (Bi et al. 2003;
Yusà et al. 2006; Duan et al. 2007; Nardocci 2010; Di Vaio et al. 2016).
In the atmosphere, PAHs can be present in both the gas phase and the particulate
phase, so that their distribution is related to the physicochemical properties.
The low molecular weight PAHs (two to three aromatic rings) are preferably in
the gas phase, the intermediate molecular weight PAHs (four aromatic rings) are
distributed in both the gas and particulate phases, and the higher molecular
weight PAHs (five to six aromatic rings) are found adsorbed on atmospheric
particles (WHO 2010; Barrado et al. 2013; Amarillo and Carreras 2016; Nyiri
et al. 2016). Other factors that may influence the predisposition of PAHs in
the atmosphere are the essential climatic parameters such as ambient temp-
erature, solar radiation, relative humidity, and wind (Amarillo and Carreras
2016; Mohammed et al. 2016).
PAHs, because of their characteristics, are prone to resist photolytic, chemical,
and biological degradation. Also, they can bioaccumulate, especially in species at
the top of the food chain, because they have low solubility in water and high lipid
solubility (Bogdal et al. 2013; Abdel-Shafy and Mansour 2016).
In general, all organic compounds containing carbon and hydrogen can
serve as precursors of PAHs. The formation of PAHs in the atmosphere occurs
mainly through the mechanisms of pyrolysis and pyrosynthesis. Pyrolysis
occurs when organic compounds reach high temperatures and are converted
into small unstable molecules (decomposition). Pyrosynthesis is the result of the
recombination of these small molecules with other radicals, which form
larger and more stable PAH molecules (Bettin and Franco 2005; Albuquerque
et al. 2016).
The main sources of PAH emissions into the atmosphere are the incomplete
combustion of organic material from both natural sources (forest fires and volcanic
eruption) and anthropogenic sources (biomass burning, coal and oil combustion, and
mainly vehicular emissions) (Migliavacca et al. 2012; Albuquerque et al. 2016;
Di Vaio et al. 2016). Anthropogenic sources, in general, are the ones that most
contribute to the emission of PAHs. These sources, depending on the process and
type of fuel used, generate different amounts and types of compounds. In urban
areas, the most important source is vehicle emissions, influenced by a variety of
factors such as fuel type, vehicle speed, ambient temperature, catalyzers, and engine
settings. The use of diesel is considered the most critical because its soot particles
have a large surface/volume ratio and reactive surfaces, thus attracting condensable
materials such as PAHs, shortly after emission to ambient air (Agudelo-Castañeda
and Teixeira 2014).
Some PAHs are characteristic markers of certain pollutant sources, as can be
observed in Table 1.
Human exposure to PAHs occurs primarily through the inhalation of contaminated
indoor and outdoor air, water intake, soil, dust, contaminated food, skin contact, and
smoking habits. The lungs and the respiratory system itself are the major routes of
exposure in the body after inhalation of aerosols and particles. The structure, size, and
chemical nature of the particles, as they are deposited in the airways, will determine if
the PAHs will be deposited in the lungs and if they will be lodged in the alveoli or
expectorated (WHO 2010).
Table 1 PAH markers and their respective emission sources

Polluting
source PAHs emitted Reference
Combustion Fluorene, phenanthrene, Wang et al. (2009), Karavalakis et al.
of diesel fuel acenaphthylene, anthracene, chrysene, (2010)
pyrene, indene(1,2,3-cd)pyrene,
fluoranthene, benzo(a)pyrene, benzo
(b)fluoranthene, benzo(k)
fluoranthene, and benzo(a)anthracene
Combustion Pyrene, phenanthrene, fluoranthene, Miguel et al. (1998), Devos et al.
of gasoline acenaphthylene, benzo(a)pyrene, (2005), Ravindra et al. (2008),
chrysene, benzo(ghi)perylene, and Pengchai et al. (2009), Wang et al.
dibenzo(a, h)anthracene (2009)
Dust Benzo(b)fluoranthene, benzo(k) Fang et al. (2004), Liu et al. (2007),
fluoranthene, benzo(a)anthracene, Zheng et al. (2016)
fluorene, benzo(ghi)perylene, benzo
(a)pyrene, pyrene, and chrysene
Combustion Acenaphthylene, anthracene, Bzdusek et al. (2004)
of wood phenanthrene, benzo(a)pyrene,
pyrene, fluoranthene, benzo(b)
fluoranthene, and
benzo(k)fluoranthene
Combustion Chrysene, anthracene, benzo(b) Li et al. (2006), Wan et al. (2006),
of coal fluoranthene, benzo(k)fluoranthene, Chang et al. (2006), Agudelo-
fluoranthene, pyrene, phenanthrene, Castañeda and Teixeira (2014)
benzo(a)anthracene, benzo(a)pyrene,
indene(1,2,3- cd)pyrene, and benzo
(ghi)perylene
Industries in Fluoranthene and indene(1,2,3-cd) Ravindra et al. (2006)
general pyrene
Steel Anthracene, phenanthrene, benzo(a) Ravindra et al. (2006)
industries pyrene, benzo(ghi)perylene, and
chrysene
Therefore, because of their characteristics, PAHs have carcinogenic, mutagenic,

and teratogenic properties, thus posing a severe threat to the health and well-being of
human beings.
Impacts of Air Pollutants
In the atmosphere, the effects of pollutants include, in addition to damage to

vegetation, soil, and materials, the increase of particles, thus reducing visibility
and inhibiting solar radiation received; the increase of the concentrations of gaseous
pollutants that absorb longwave radiation and increase the surface temperatures; and
also the alteration of precipitation, reducing the amount of rain due to the increase of
particles that function as a cloud condensation nucleus. In human health, exposure to
air pollutants can affect the respiratory system, cardiovascular system, and nervous
system, leading to increased mortality and morbidity (WHO 2016).
The means of exposure of humans to PAHs are the inhalation of contaminated
indoor and outdoor air, the intake of water, soil, contaminated food and dust, skin
contact, and even smoking habits. The main route of exposure of PAHs in the body is
the lungs, after inhalation of aerosols and particles. As soon as they are deposited in
the airways, the structure, size, and chemical nature of the particles will define the fate
of PAHs, which may remain in the lungs, be lodged in the alveoli, or be expectorated
(WHO 2010). HPAs have carcinogenic, mutagenic, and teratogenic properties, thus
posing a threat to the health and well-being of humans. The most significant effect
expected on health is the excessive risk of lung cancer (Stockholm Convention 2001;
Abdel-Shafy and Mansour 2016). Other diseases associated with exposure to PAHs
include bronchitis, asthma, heart disease, and gastrointestinal disorders, among
others (ATSDR 1995; Cai et al. 2017).
Given the main impact of PAHs on humans and lung cancer and the difficulty of
assessing exposure to the PAHs mixture, due to their presence as a mixture of several
compounds, benzo[a]pyrene is used as an indicator of the presence of HPA in
the environment, from the calculation of benzo[a]pyrene equivalent (BaPeq). To
evaluate the exposure of the “increased lifetime risk of cancer” or excess lifetime
cancer risks (ELCR), it is considered the risk unit for lung cancer (UR)
8.7105 ng m3 of B [a] P, this means an estimated 8.7 cases of cancer related to
BaP exposure in a population of 100,000 people when exposed to a concentration of
1 ng m3. To associate ELCR due to exposure to a given BaPeq concentration above
1 ng m3, the total level of BaPeq is multiplied by UR (OEHHA 2003; WHO 2010).
The contribution of PAHs to ecosystems occurs through dry and humid atmo-
spheric deposition, reaching vegetation, soil, and water. Thus, these matrices are
compartments that can retain and accumulate PAHs (Rodriguez et al. 2010, 2015).
The cuticle of plant materials (Fig. 1), rich in lipids, is susceptible to the accumu-
lation, mainly by atmospheric deposition, of these PAHs, which are lipophilic and
are, thus, adsorbed in organic fractions.
When released into the atmosphere, 44% of PAHs are deposited in the vegetation,
41% are transported or undergo some transformation in the atmosphere, and 10% are
deposited in the soil and 5% in the water. Also, PAHs present in vegetation and soil
are susceptible to undergo revolatilization, returning to the atmosphere or reaching
the soil and water, consequently (Fig. 2) (Lehndorff and Schwark 2004).
Figure 2, in addition to illustrating the deposition of PAHs in the ecosystem,
illustrates how adhesion of PAHs occurs in the epicuticular wax and the stomatal
cavity of the leaf surface. The compounds present in the vapor phase can be absorbed
by stomatal absorption and/or diffusion through layers of wax and membranes.
However, the PAHs associated with the particles accumulate in the lipophilic
epicuticular wax layer on the leaf surface (Holoubek et al. 2000; Bakker et al.
2001; Lehndorff and Schwark 2004; Belis et al. 2011).
When the absorption of PAHs occurs by plant tissues, the plant organism is
susceptible to an accumulation considered irreversible and potentially harmful.
However, when PAHs are adsorbed on the cuticle surface, this character becomes
Foliar Uptake
Heavy metal deposition and penetration via cuticular cracks

(major physical barrier of foliar metal uptake)
Shoot-root metal transfer
Root-shoot metal transfer
Epidermis
Heavy metal transfer towards
vascular bundle
Heavy metal penetration Heavy metal transfer towards roots

via stomata via xylem and phloem
Root Uptake
Fig. 1 Routes of entry of metallic pollutants in plants. (Source: Adapted from Shahid et al. 2017)
Fig. 2 Model of deposition and transport of PAHs in the atmosphere and modes of accumulation
thereof, associated with the gas fraction and particles. (Source: Adapted from Lehndorff and
Schwark 2004)
reversible, and the compounds may even return to the atmosphere through
revolatilization or be degraded by photolysis, limiting leaf accumulation (Kaupp
et al. 2000; Alkio et al. 2005; Oguntimehin et al. 2008; Desalme et al. 2013; Wang
et al. 2014). The capacity to capture PAHs from air by different plant species, as well
as the performance of an important role in their absorption and accumulation, is
affected by the plant metabolism (gas exchange), by the leaf morphology (e.g.,
surface area, trichomes, and roughness), and by anatomy (e.g., density of stomas
and presence of cuticular waxes and polymeric lipids) (Bakker et al. 2000, 2001; Li
and Chen 2014; De Nicola et al. 2017).
The understanding of the accumulation of PAHs in plants can be used as an easy-
to-operate tool to identify emission sources and to estimate the levels of contamina-
tion in the ambient air (Lodovici et al. 1998; Librando et al. 2002; Marsili and
Stracquadanio 2011). A bioindicator plant, capable of detecting the accumulation of
trace elements, sulfur, fluorides, as well as PAHs, has been widely used and seems to
be satisfactory, mainly in Europe, the grass L. multiflorum (Carminitti et al. 2007;
Klumpp et al. 2009; Rodriguez et al. 2010, 2015; Rinaldi et al. 2012; Pereira
et al. 2013).
Many metals occur naturally at low levels in the environment and are considered
essential nutrients for humans. However, even at low concentrations, some metal
ions, as well as those in high concentrations, may have harmful effects on human
health and the environment (CETESB 2015; Bonanno et al. 2017).
A wide range of processes and pathways may emit metals into the environment,
with atmospheric emissions probably being the most important regarding human
health, both concerning the quantities and concentrations involved and the general-
ized dispersion and cumulative exposure. Among the various metals found in the
atmosphere are aluminum (Al), barium (Ba), cadmium (Cd), copper (Cu), lead (Pb),
chromium (Cr), iron (Fe), manganese (Mn), mercury (Hg), nickel (Ni), and zinc
(Zn) (Illi et al. 2017).
Al, the third most abundant element in the earth’s crust, can become toxic to
terrestrial and aquatic species because it has its solubility increased in acidic envi-
ronments. Its properties make it widely used in different industrial sectors such as
metallurgical, packaging, constructions, electrical and chemical productions, as well
as a corrosion inhibitor. Its compounds are used in water treatment, sugar refinement,
wood preservation, papermaking, and leather tanning. The average global concen-
tration of Al in the air in remote regions is in the range of 46–70 ng m3, while in
polluted areas, it is 1300 ng m3 (Adachi and Tainosho 2004; Kabata-Pendias and
Mukherjee 2007; Darus et al. 2012).
Ba, a common and ubiquitous element in the earth’s crust, is widely used in the
production of bricks, tiles, glass, ceramics, synthetic rubber (tire manufacturing),
automotive lubricants, and paints. Another use of Ba compounds is in the medical
field, for example, the use of contrast in X-ray examinations. The range of Ba
concentrations in the air in remote and polluted regions of the world is reported as
0.02–0.73 and 0.2–90 ng m3, respectively (Kabata-Pendias and Mukherjee 2007;
Darus et al. 2012; Bauerová et al. 2017).
Metal that rarely occurs in nature, Cd, is considered one of the most ecotoxic
metals presenting adverse effects on the biological processes of humans, animals,
and plants. It is produced as a by-product in mining and refinement of Zn and
recovered from recycled materials like Zn-Cd batteries. It is used in the production of
Ni-Cd and Ag-Cd batteries, as a yellow pigment and as coating of stabilizers, and
because of its physicochemical properties, it is added to the alloys as stabilizers for
various plastics, mainly to protect against sunlight, chemical attack, or heat degra-
dation. The average global concentration of Cd varies between 0.2 and 0.4 ng m3 in
remote regions, whereas in polluted sites, it is 20 ng m3 (Gajghate and Bhanarkar
2005; Kabata-Pendias and Mukherjee 2007; Gunawardana et al. 2012).
Cu is a very versatile metal, due to its properties, involving a wide variety of
applications. Its use ranges from the production of various materials such as copper
wires for electrical current conductivity, manufacturing of motors, electrical equip-
ment, coins, art objects, ammunition, even fertilizers, and pesticides. Also due to its
bacteriostatic properties, it is also added to animal feed. The concentration of Cu in
air ranges from 0.03–0.06 ng m3 around the South Pole to 4900 ng m3 in the
industrialized regions (Adachi and Tainosho 2004; Kabata-Pendias and Mukherjee
2007; Kar et al. 2010; Darus et al. 2012).
Pb, although possessing high toxicity, is also very useful. Its emission in the 1970s
and 1980s was mainly due to the use of gasoline containing Pb. Its control began in
the 1990s, when a regulation was created to prohibit the use of Pb in gasoline in most
countries, with exceptions such as Africa, which continued to produce gasoline with
this compound. Currently, the main use of Pb worldwide is lead-acid batteries used in
automotive vehicles, as well as welding Pb-Sn, metal alloys, chemicals, cables, and
lead weights, among others. The concentrations of Pb in the air around the South Pole
range from about 1 ng m3 to above 10,000 ng m3 in urban/industrial areas
(Espinosa et al. 2001; Adachi and Tainosho 2004; Kabata-Pendias and Mukherjee
2007; Kar et al. 2010).
The metallic element Cr is mainly used in metallurgical, refractory, and chemical
industries, in the manufacture of stainless steel, pigmentation of paints, varnishes,
enamels, papermaking, wood preservatives, and leather tanning (the main source of
pollution). The mean global values of Cr in the air in remote areas are reported as
0.5–0.6 ng m3 and in polluted regions as 40 ng m3. However, the Cr variation in
the air is from 0.003 ng m3 in the South Pole to more than 1000 ng m3 in industrial
areas (Adachi and Tainosho 2004; Gajghate and Bhanarkar 2005; Kabata-Pendias
and Mukherjee 2007; Darus et al. 2012).
Mn, one of the most abundant elements in the lithosphere, is a member of the Fe
family and is associated with geochemical processes. Its use occurs mainly in the
metallurgical industry (manufacture of steel and alloys to provide hardness and
toughness and acts as an antioxidant) and production of pigments, ceramics, and
glass and as additive to increase octane in gasoline, replacing Pb in the form of the
organic compound methylcyclopentadienyl manganese tricarbonyl. Mn concentra-
tions in the air range from <0.02 ng m3 in the Southern Pole region to 900 ng m3
in industrial regions, with the mean annual concentration being approximately
2 ng m3 (Kabata-Pendias and Mukherjee 2007; Gunawardana et al. 2012; Moreno
et al. 2013).
The most important metal Fe, one of the main constituents of the lithosphere, is
in an intermediate position between macro- and micronutrients in plants, animals,
and living beings, playing a particular role in the behavior of several other metals.
When present in metal alloys, it is used in various chemical, steel, and metallurgical
industries. Besides, it is also used in the manufacturing of tools, transportation, and
construction sector. Fe concentrations vary widely from 50 to 14,000 ng m3 in the
atmosphere of different cities in several continents and are clearly associated with
industrial activities. The mean concentrations of Fe in remote regions of the world
range from 60 to 70 ng m3, whereas in polluted areas they range from 130 to
14,000 ng m3 (Adachi and Tainosho 2004; Kabata-Pendias and Mukherjee 2007;
Darus et al. 2012; Gunawardana et al. 2012).
Hg is not abundant in the earth’s crust and it is present in fossil fuels. It is
mainly used in the production of caustic soda and chlorine. Although there is
a tendency to replace it with other metals in various productions and activities,
Hg is still used in dental treatments, lamps, thermometers, batteries, manometers,
electric conductors, pesticides, and paints. The concentrations of Hg in the
atmosphere in remote regions vary from 0.01 to 0.06 ng m3 and in polluted
areas from <0.09 to 38 ng m3 (Kabata-Pendias and Mukherjee 2007; Kim et al.
2016; Zhang et al. 2017).
The emission of Ni into the atmosphere occurs from the combustion of coal
and petroleum combustion products. Its use is employed in a variety of metal alloys
for the aircraft and sheet industries, stainless steel, magnetic components, and
electrical equipment. Ni alloys are applied in medicine and food technology, and
their compounds are used as colorants in ceramic and glass products and in Ni-Cd
batteries. The median Ni concentration in the air of the remote regions of the world is
90 ng m3 and of the polluted regions is 60 ng m3 (Gajghate and Bhanarkar 2005;
Kabata-Pendias and Mukherjee 2007; Darus et al. 2012; Moreno et al. 2013).
Zn, which serves as corrosion protection for steel and other metal components, is
widely used in industries. Important in various alloys, it serves as a catalyst in the
production of rubber, pigments, plastics, lubricants, and pesticides. Zn compounds
have dental and medical applications. In general, low and constant levels of Zn are
observed in the air. The median global concentrations of Zn in the air are estimated at
7 and 900 ng m3 for remote and polluted sites, respectively (Adachi and Tainosho
2004; Gajghate and Bhanarkar 2005; Kabata-Pendias and Mukherjee 2007; Kar
et al. 2010; Gunawardana et al. 2012).
The occurrence of metals in the air is predominantly associated with particulate
matter (PM), since most of them, with exceptions such as mercury (Hg), have low
volatility in environmental conditions. Both metal toxicity when inhaled and the
extent of dispersion through atmospheric transport and residence time in the atmo-
sphere can be influenced by the size of the particles. Understanding trace metal levels
in the air is essential for reasons such as understanding its global biogeochemical
cycle and its environmental and health impacts (Seinfeld and Pandis 2006; Witt
et al. 2010).
The sources of emission of metals into the atmosphere may be natural – such as
rocks, minerals, volcanoes, and inclemencies – or anthropogenic, such as fossil
fuel combustion, wood, high temperature, natural and industrial processes, waste
incineration, and vehicular activities (fuel combustion, tire abrasion, brake wear,
and the resuspension of road dust that can contaminate the atmospheric environ-
ment) (Ahmed et al. 2016; Chandra et al. 2016; Bonanno et al. 2017). The metals
of anthropogenic origin (As, Cd, Cr, Cu, Mn, Ni, Pb, Zn, and Hg) tend to accumulate
in the fine particulate material, whereas the natural origin ones, components of
the earth’s crust (Na, K, Mg, Ca, Al, and Fe), tend to accumulate in the
coarse particulate material (Alves 2014; Ahmed et al. 2016; Chandra et al. 2016;
Gajbhiye et al. 2016).
It is observed, therefore, that in environments impacted by vehicular traffic, when
compared to industrialized regions, Zn, Ba, Cu, and Sb levels are generally relatively
high. The occurrence of these elements is due to the influence of the decomposition
of the tires on the highways (Zn-Ba) and the abrasion of the brakes (Cu-Sb). As a
result of the resuspension of the deposited material on the road, high concentrations
of titanium (Ti), strontium (Sr), and zirconium (Zr) are also recorded. In addition,
varying amounts of Pb, Fe, Cu, Zn, Ni, and Cd can be observed as a consequence of
the exhaust emissions of gasoline and diesel from vehicles (Kabata-Pendias and
Mukherjee 2007; Schneider 2016).
The release of Zn into the atmosphere occurs through mining activities and the
burning of fossils or fuel additives. Combustion of domestic waste, fossil fuels,
and refinery are possible sources of Cd, and are still possible Pb sources in the
industrial processes and solid fuels, as well as painting processes, alloys, and
industries of plastic and rubber (Kabata-Pendias and Mukherjee 2007; Chandra
et al. 2016).
Because they are not capable of decomposing or destroying themselves,
metals become bioaccumulative and persistent in the environment and, together
with their toxicity, become harmful to terrestrial and aquatic ecosystems and,
therefore, to human and animal life (CETESB 2015; Ahmed et al. 2016; Bonanno
et al. 2017).
According to toxicological studies, each metal can specifically affect a particular
living being, and the chemical form of this element is a factor that contributes
significantly to its toxicity. When the metals are in the form of cations or bound to
short organic chains, they become more bioavailable and, hence, more harmful.
Thus, metal ions, for example, form complexes with a large number of ligands and
may exert influence on biological functions (Lima and Merçon 2011). When asso-
ciated with atmospheric PM, metals can be absorbed into lung tissues and cause a
variety of chronic and acute effects on human health. Among these effects are cancer
and toxic effects on the kidneys and the immune, nervous, and respiratory systems,
causing, for example, diseases such as asthma, bronchitis, rhinitis, and sinusitis
(CETESB 2015; Izhar et al. 2016; Wan et al. 2016).
Some studies have shown that even metals such as Fe, Zn, and Cu can cause
adverse health effects in moderate concentrations, although traces of these transition
metals are generally considered to be harmful to human health. By entering living
organisms at concentrations above that allowed by regulatory normativity, Fe and Cu
can damage proteins and alter the DNA sequence, disrupting the respiratory immune
response in exposed individuals (González et al. 2017).
According to the US Environmental Protection Agency (USEPA) and the Inter-

national Agency for Research on Cancer (IARC), based on epidemiological
and experimental studies showing an association between exposure and cancer
incidence in humans and animals, metals like As, Cd, Cr, Pb, and Hg are classified
as carcinogenic or likely carcinogenic (Tchounwou et al. 2012).
Due to the bioaccumulative, persistent, and toxicological properties of the
metals in the environment, and their consequences, mainly to humans, as previously
described, it is important to monitor these elements in the atmosphere in order to
seek improvement or maintenance of the air quality, as well as life quality. Thus,
among the several methods available to evaluate metallic ions in the air, the
biomonitoring using plants has been shown to be efficient in its use (Norouzi et al.
2016; Illi et al. 2017; Shahid et al. 2017).
The contribution of metals in plants occurs by both adsorption and internalization
through the cuticle and by penetration through stomatal pores. By penetrating the
leaf surface, the metabolic processes occur, and then the metal is transported through
the plasma membrane and protoplast and may reach the roots (Kabata-Pendias 2011;
Shahid et al. 2017).
Physical, chemical, and biological mechanisms are involved in the deposition of
the metals in the leaves. The physical adsorption is related to the mechanical capture
of the metals present in the particulate matter by the foliage, taking into account the
physical characteristics of the vegetation (trichomes, superficial roughness, epicu-
ticular wax layer). The chemical and biological factors of the adsorption of metals
take into account the capacity of retention/deposition of metals by the cuticle of the
plant, being influenced by the permeability of the cuticle and the chemical charac-
teristics of the metals. Therefore, it is observed that metals associated with fine
particles penetrate into the leaves, whereas those associated with the coarse particles
become trapped in the superficial wax (Shahid et al. 2017). The metal pollutants are
retained superficially in the leaves, subject to leaching through winds and rainwater
(Kabata-Pendias 2011).
Among the species of plants evaluated systematically as bioindicators of
metallic pollutants in the air, in urban and industrial sites, are several lichens,
epiphytes, and vascular plants (Vianna et al. 2011; Wannaz et al. 2012; Abril et al.
2014; Sutton et al. 2014). Caggiano et al. (2001), De Temmerman et al. (2007),
Franzaring et al. (2007), and Klumpp and Ro-Poulsen (2010) used in their studies
the vascular species L. multiflorum, showing the high accumulating potential of
these species.
Environmental Monitoring: Air Pollution
Atmospheric monitoring is an integral part of an effective air quality management

system, where a systematic and long-term assessment of the levels of pollutants
present in atmospheric air is carried out, using quantification and determination of
pollutant types. Among the main reasons why these data are collected are the
assessment of the extent of pollution, the provision of air pollution data to the
general public, support for the implementation of air quality goals or standards,
evaluation of the effectiveness of the strategies of emission control, the provision of
information on trends in air quality and data for the assessment of air quality models,
and support for research, such as long-term studies on the effects of air pollution on
health (WHO 2010). Also, atmospheric monitoring can be divided into emissions
monitoring, which measures the concentration or emission rate of pollutants from
chimneys or pipelines, and air quality monitoring, which measures and quantifies
concentrations of pollutants “present in the environment,” excluding “where people,
animals and plants are inserted.”
In order to monitor and evaluate air quality, the commonly used sampling methods
are active monitoring, passive monitoring, automatic analyzers, and biomonitoring.
The selection of the method to be used must be carried out with care, observing which
one is most appropriate, taking into account the main uses of the data, the initial
investment costs for equipment, operating costs, system reliability, and ease of
operation. The equipment should be able to guarantee that the generated data meet
the objectives of the monitoring, in particular, that can be compared with the legal
standards of air quality.
Methodologies Related to Environmental Toxicology
Active and Passive Biomonitoring
Tradescantia pallida var. purpurea has been used as a biomonitor for the
genotoxicity of atmospheric air through active monitoring when the plants are
taken to the sites to be evaluated (Savóia et al. 2009; Costa and Droste 2012;
Blume et al. 2014; Cassanego et al. 2015; Costa et al. 2016) or through passive
monitoring, when naturally occurring plants in the monitored sites are evaluated.
The active biomonitoring is a tool used to evaluate the air quality of environments
with different magnitudes of environmental impacts and consists of the systematic
analysis of the responses of organisms introduced in a standardized way in the
natural environment for a certain period (Markert 2007). The accumulating capacity
of pollutants by Tradescantia pallida var. purpurea has been little explored until
now (Santos et al. 2015), and the information is based only on the leaf content of
these elements.
For the Bioassay Trad-MCN the plants of Tradescantia pallida var. purpurea
must be grown in plastic containers (37 20 20 cm) containing 4 kg of
commercial soil from the same lot and kept in an external environment. The plants
need to be watered three times a week and monthly applied 100 mL of N-P-K
(nitrogen-phosphorus-potassium) fertilizer solution in the proportion of 10-10-10
(v-v-v), following the method described by Thewes et al. (2011). For exp-
osure to atmospheric air, the buds should be 10–15 cm in length with young
inflorescences.
The buds should be exposed partially immersed in containers with 2 L of distilled
water, remaining for 24 h for adaptation (Cassanego et al. 2014), in an
air-conditioned room with a temperature of 26 1 C. Afterwards, the containers

with the adapted branches must be packed in thermal boxes and transported to the
sample points where they will be exposed for a period of 8 h. Later, in an
air-conditioned room, the buds should be recovered in distilled water for another
24 h (Cassanego et al. 2014).
After the recovery period, flower buds should be fixed in ethanol/acetic acid
(3:1 v:v) for 24 h and then stored in 70% ethanol under refrigeration (4 C). For the
preparation of the slides and analysis of the cells and micronuclei (MCN), flower
buds must be dissected and the anthers macerated with 1% acetic carmine. Three
hundred young cells of tetrad stage pollen grains must be counted on each slide and
the number of MCNs recorded on a total of ten slides under 400 magnification
optical microscopy. The MCNs considered must have a diameter of less than
one-third of the nucleus and be separated and similarly stained (Grisolia 2002).
The frequencies of micronuclei must be expressed in MCN/100 tetrads (Thewes
et al. 2011).
The Trad-MCN bioassay with Tradescantia pallida var. purpurea provides infor-
mation on areas of genotoxic risk and also allows a record of the effects of complex
mixtures of pollutants on living organisms.
Lolium multiflorum Lam. (ryegrass) may be another bioindicator used to evaluate
the accumulation of toxic substances in the environment, including heavy metals,
sulfur, fluorine (Klumpp et al. 2009; Rodriguez et al. 2010), and PAHS (Rinaldi et al.
2012; Pereira et al. 2013). This species has a high capacity for the accumulation of
toxic substances, as well as a high tolerance against most air pollutants, without
showing any visible damage due to environmental pollution levels, acclimating very
well in temperate regions (Klumpp et al. 2009). Relevant information concerning air
toxicity at the site where this plant is inserted, as well as the indication of possible
environmental risks, may be provided by the presence or absence of toxic substances
in the species (Klumpp et al. 2001). The use of L. multiflorum in air biomonitoring
has been occurring in several parts of the world, including Brazil, for several years,
proving its effectiveness and usefulness.
Lactuca sativa (lettuce seeds) can also be used for the toxicity tests of particulate
matter. The test consists of exposing the species to a soluble solution of the
particulate material after extraction with two ultrapure water filters by ultrasound
technique. Exposure of the organism is performed with the liquid samples (soluble
fraction), in the concentration of 100%, maintaining a control group, exposed only to
ultrapure water. The assays use the method of direct exposure of the organism to a
filter paper moistened with the sample to be tested, a methodology adapted from
USEPA guide (1996). The tests are performed in triplicate. At the end of the
incubation, the number of seeds germinated is counted, and the root length of the
germinated seeds is measured. For the results to be acceptable, the average germi-
nation in the controls should be at least 90%. Seed germination is defined as growth
of 5 mm or more from the root. The results are used to establish two toxicity indexes:
seed germination (SG) and root growth (RG). SG represents the normalized residual
percentage of seeds germinated after the experiment. The RG represents the nor-
malized residual growth of the roots of the germinated seeds by a test. Indexes
are established by the following scale: (a) 0 to 0.25 low toxicity, (b) 0.25 to 0.5
moderate, (c) 0.5 to 0.75 high, and (d) 0.75 to 1 very high. The values of
RG > 0 indicate stimulation of seed growth (Bagur-González et al. 2011).
Comparative Analysis of Different Studies and Parameters:

Environmental Toxicology and Atmospheric Pollution
In a study to verify the reliability of the use of L. multiflorum for the biomonitoring
of metals in the air in an industrial area in Southern Italy, Caggiano et al. (2005) have
found medium concentrations for metals Cd, Cu, Fe, Mn, Ni, Pb, and Zn, ranging
from 0.29 mg kg1 (Cd) to 215 mg kg1 (Mn), and metals which presented the
highest concentrations according to the author were Mn, Fe, and Zn. Rodriguez et al.
(2010) evaluating the ability of L. multiflorum to accumulate metals at sites with
different vehicular traffic influences in Stuttgart, Germany, have found average
concentrations of metals ranging from 4.11 mg kg1 (Pb) to 3150 mg kg1 (Fe) in
a site with a high impact of vehicular traffic and from 2.33 mg kg1 (Pb) to
3160 mg kg1 (Fe) in a place with a moderate impact of vehicular traffic. Of the
metals evaluated, the ones with the highest concentrations were Fe, Mn, and Zn.
Alves et al. (2015) and Illi et al. (2017) used L. multiflorum to evaluate air quality
by determination of metals in the Rio dos Sinos River Basin Region, Southern
Brazil, between 2013 and 2014. Alves et al. (2015) identified Pb, Cr, and Zn in
the ryegrass leaves at concentrations 13.58, 5.26, and 88.80 mg kg1, respectively, at
their place of study, showing a very high level of pollution (Class 4), according to the
classification proposed by Klumpp (Klumpp et al. 2004) (Table 2). Illi et al. (2017)
in their study sites verified a similar profile, where Pb, Cr, Zn, and Cu metals were
also found at high levels, revealing a very high level of pollution.
Meincke (2018), in the same study region of Alves et al. (2015) and Illi et al. (2017),
also using L. multiflorum, determined air quality through determination of metals and
PAHs from June 2015 to May 2017. For metals, the author found average concentra-
tions at sampling points ranging from 0.003 mg kg1 (Pb) to 417.05 mg kg1 (Al). High
concentrations of Cd, Cr, and Pb implied a very high level of pollution by metals at the
evaluated points. For PAHs, mean concentrations ranged from 0.72 to 22.67 ng g1, the
total sum was 1365.41 to 1838.57 ng g1, and the mean total was 1184.08 ng g1.
In Cubatão, in the state of São Paulo, Brazil, Rinaldi et al. (2012), in three
different periods, found the following values of the total sum of PAHs in
L. multiflorum: 7456 ng g1, 9156 ng g1, and 3778 ng g1. Carminitti et al.
(2007) verified in his study in São Paulo that the total sum of PAHs at ryegrass for
the two sites sampled were 826.28 ng g1 and 798.94 ng g1 in winter and
1038.6 ng g1 and 371.36 ng g1 in summer.
Finally, Rodriguez et al. (2015), when evaluating an industrial area in Córdoba,
Argentina, using L. multiflorum, found mean concentrations between 0.21 ng g1
and 100 ng g1 in the dry season (autumn) and between 0.51 ng g1 and
75.60 ng g1 in the rainy season (spring). The mean total concentrations for the
two periods, dry and rainy, were 146.17 ng g1 and 137.42 ng g1, respectively.
51
Table 2 Studies and parameters: bioindicator, method of the collection, and analysis
Parameter Bioindicator Method collection Method analysis Local Author
PAHs Ryegrass Seeding (0.60 g) Soxhlet extraction Canoas, São Leopoldo e Campo Bom – Rio Meincke (2018)
Germination (15 days) (CH2Cl2/24 h) Grande do Sul, Brazil
Exposure (30 days) Cleanup (silica gel
column)
Determination by
GC/MS
PAHs Ryegrass Seeding Soxhlet extraction Cubatão – São Paulo, Brazil Rinaldi et al. (2012)
Germination (CH2Cl2 and C6H14/24 h)
Exposure (28 days) Centrifugation
Determination by
HPLC
PAHs Ryegrass Seeding Soxhlet extraction São Paulo City – São Paulo, Brazil Carminitti et al. (2007)
Germination (28 days) (CH2Cl2/24 h)
Pruning and fertilization on Determination by
the 14th day of germination GC/MS and GC/FID
Exposure (28 days)
PAHs Ryegrass Germination (28 days) Extraction by ultrasound Cordoba – Argentina Rodriguez et al. (2015)
Pruning and fertilization (C6H14 e C3H6O/30 s)
Exposure (28 days) Cleanup (sartorius filters)
Determination by HPLC
Metals Ryegrass Seeding Drying (70 C/72 h) Canoas, São Leopoldo e Campo Bom – Rio Meincke (2018)
Germination (15 days) Microwave digestion Grande do Sul, Brazil
Environmental Toxicology and Air Pollution: A Comparative Analysis of. . .
Exposure (30 days) (HNO3, 200 C/30 min)

Determination by FAAS
Metals Ryegrass Seeding (10 g) Microwave digestion Tito – Basilicata, Italy Caggiano et al. (2005)
Germination (7 days) (HNO3 e HF)
Exposure (15 days) Determination by
FAAS e GFAAS
1261
(continued)
1262
Table 2 (continued)
Parameter Bioindicator Method collection Method analysis Local Author
Metals Ryegrass Seeding (0.60 g) Reduction to ashes Stuttgart – Germany Rodriguez et al. (2010)
Germination (500 C/4 h)
Pruning and fertilization Acid digestion
Exposure (28 days) (HCl e HNO3)
Determination by XRF
Metals Ryegrass Seeding (0.30 g) Drying (70 C/72 h) Campo Bom – Rio Grande do Sul, Brazil Alves et al. (2015)
Germination (14 days) Microwave digestion
Metals Ryegrass Seeding (0.30 g) Drying (70 C/72 h) Canoas, São Leopoldo, Novo Hamburgo e Illi et al. (2017)
Germination (14 days) Microwave digestion Campo Bom – Rio Grande do Sul, Brazil
G. M. da Costa et al.
Final Considerations
In order to evaluate the environmental quality of a given region, we must obtain

information that is integrated between the biotic and abiotic factors that govern the
functioning of the ecosystem. In this sense, the combined use of different method-
ologies to identify air quality degradation is a challenge, but when used separately,
these methodologies may not adequately reflect ecosystem responses. In addition,
integrated environmental quality information can complement studies related to
environmental toxicology, further strengthening results that are relevant to environ-
mental health.
The potential bioaccumulator of trace elements in Tradescantia pallida
var. purpurea and Lolium multiflorum suggests the continuous monitoring of atmo-
spheric air quality in metropolitan regions. Besides, the use of L. multiflorum is a
low-cost method and, like the small volume sampler, is easy to apply and can be
widely used as a tool to evaluate the effects of atmospheric pollutants in urban, rural,
and semi-urban areas and also can be used in a complementary manner to other
standard air quality research methods. The importance of the use of environmental
parameters is associated with its use as an instrument for planning and managing
urban spaces, serving to make better use of natural resources and also as a preventive
measure against environmental degradation, besides boosting the generation of data
related to environmental degradation so that they can be used to support environ-
mental toxicology studies and consequently environmental risk probability studies.
Cross-References
▶ Air Pollution
▶ Integrated Evaluation of Quantitative Factors Related to the Environmental
Quality Scenario
▶ Monitoring and Risk Analysis of PAHS in the Environment
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The Effects of Atmospheric Pollution
in Respiratory Health 52
Sandra Magali Heberle, Gustavo Marques da Costa, Nelson Barros,
and Michele S. G. Rosa
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1272
Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1275
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1275
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1282
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1283
Abstract
This research consists of a review developed based on studies on the association
between air pollution and respiratory health, more specifically, on the effects of
NO2 (nitrogen dioxide), particularly on bus drivers. The Revolution Industrial
accelerated the emission of pollutants from an anthropogenic origin. The air
pollution is present in the world in the most different scenarios. Approximately
50% of the planet’s population lives in cities and urban agglomerations and is
exposed to progressively higher levels of air pollutants. Driving vehicles in high
traffic routes can increase the level of exposure to NO2 by reducing lung capacity.
S. M. Heberle · N. Barros
Energy, Environment and Health Research Unit, FP-ENAS - UFP: University Fernando Pessoa,
Porto, Portugal
e-mail: sandra.heberle@cesuca.edu.br; nelson@ufp.edu.pt
G. M. da Costa (*)
Programa de pós-graduação em Qualidade Ambiental, Universidade Feevale, Novo Hamburgo, RS,
Brazil
M. S. G. Rosa
Pontifícia Universidade Católica do Rio Grande do Sul – PUCRS, Porto Alegre, Brazil
e-mail: milkasg@gmail.com

https://doi.org/10.1007/978-3-319-73645-7_171
1272 S. M. Heberle et al.
Therefore, studies in the Medline and B-on databases, which have evaluated the
levels of NO2 concentration due to the emission of motor vehicles and their
effects on human health, are being sought. On the other hand, the lists of
references of the selected articles were also revised, allowing in this way to
broaden the research carried out. The research period included studies published
until July 2016, with a series of articles, abstracts, and full texts which were
screened to identify suitable studies and, therefore, to select the research to be
used. The inclusion criteria for articles were those that analyzed the association of
NO2 and the effects on human health, particularly in bus drivers.
Keywords
Air pollution · Nitrogen dioxide · Traffic · Transport · Indoor air quality · Bus
drivers
Introduction
Atmospheric pollution is defined as the introduction into the atmosphere of any

matter or energy that will significantly alter its properties, thereby affecting the
“health” of the animal or plant species that depend on it, having contact with it, or
it may cause physicochemical changes in the mineral species that are approaching it
(World Health Organization 2002).
Air pollution has become an increasingly frequent problem in large urban centers
with technological developments, increasing population and means of transport
Girardi (2014) and IBGE (2016). Therefore, the traffic of motor vehicles, which
provides an extremely important contribution to the population, becomes harmful
due to the emission of a series of polluting compounds (Arbex et al. 2012).
Emissions of pollutants by vehicles are the result of the combustion or evaporation of
the fuel as well as the wear of the various components, particularly, tires and brakes. The
most commonly used fuels for transportation are gasoline, for cars (lighter vehicles), and
diesel for buses and trucks (heavier vehicles). Fuels such as ethanol (ethanol and
methanol), gasoline, alcohol blend, natural gas (NGV), and liquefied petroleum gas
(LPG) are also used in lighter vehicles (Loureiro 2005). The human being is highly
exposed to this pollution in one way or another, and most major pollutants can affect
lung function and cause severe damage to health, because air quality directly interferes
with the respiratory system, and can also reach the systemic circulation through the lungs
due to its large area of contact causing deleterious effects on organs and systems (Brook
et al. 2010; Lee et al. 2011; European Environment Agency 2013).
Pulmonary function is, therefore, an important marker of the effects of air pollution
on the exposed population, being an objective, quantitative, and early predictor of
morbidity and cardiorespiratory mortality. Studies have also shown the acute and
chronic effects of pollutants on lung function in children, adolescents, healthy adults,
and those with previous respiratory diseases (Künzli et al. 2010; Hesterberg et al. 2009).
Therefore, particulate and gaseous pollutants, emitted from various sources,
increase the symptoms of diseases, whose main effects on human health are the
52 The Effects of Atmospheric Pollution in Respiratory Health 1273
following: indisposition; irritation in the eyes, throat, and nostrils; alteration in lung
function, respiratory and cardiovascular diseases; frequent visits to the emergency
room; increased hospitalizations; and even deaths (Arbex et al. 2012; Organização
Mundial da Saúde 2008).
It is necessary, then, to establish the limits of the health effects that are intended to
be evaluated. The health effects of the population, due to exposure to environmental
pollutants, are diverse, exhibiting different intensities and manifesting themselves
with different latency times. Among the main ones, the following are mentioned:
behavioral and cognitive events; pulmonary and systemic inflammation; changes in
airway caliber, vascular tone, and heart rate control; reproductive changes; morbidity
and mortality due to cardiorespiratory diseases; and increased incidence of neopla-
sia, and considering the multiplicity of possible outcomes, it is necessary to objec-
tively explain what adverse effects are to health, clarification that will facilitate the
selection of useful events to determine the impact that some environmental modifi-
cation will have on the population (Braga et al. 2001; Yang et al. 2013).
However, although the concept of adverse or detrimental effect on human health
is widely used for the definition of risk assessment or environmental management
measures, a precise definition of the boundary between a finding of statistical
significance and a change entailing a relevant injury to health still lacks better
elucidation (Braga et al. 2001). The most widely adopted definition to characterize
an adverse health effect has been that advocated by the American Thoracic Society
(1995), which explains health impairment “as a significant medical event,” charac-
terized by one or more of the following factors:
1. Interference in activity normal of affected individuals

2. Episodic respiratory disease
3. Disabling disease
4. Permanent respiratory disease
5. Progressive respiratory dysfunction
Therefore, among the several factors that can generate the appearance of pulmo-
nary or cardiovascular diseases, air pollution is one of the important causes that has
been studied. Not only health researchers but also researchers from other areas are
concerned with exploring this relationship between pollution and the development of
respiratory diseases and thus seek preventive measures (Cardoso and Oliveira 2011;
Freitas et al. 2004; Roseiro and Takayanagui 2006). As a result, some studies have
contributed to the search for pollution prevention, and in a study conducted by
Cortes and Carneiro, in 2014, the importance of using public transportation as a form
of emission reduction is mentioned. These authors emphasize, however, the need to
evaluate the working conditions of driver subject to elevated levels of pollutants.
A study developed by Molle et al. (2013), PM2.5 and NO2 with external levels, it
was pointed out that, in the interior of the vehicle, these levels are higher and may
cause health damage to drivers who are subject to high concentrations during their
workday. The PM can act as a transport vehicle for other air pollutants, such as
pollutants, viruses, bacteria, organic substances, and odors (Tan and Zhang 2003).
Consequently, this internal combustion process, due to the decrease in pulmonary

function in children and an increased risk of respiratory tract infections (LRTIs),
especially in young children, is associated with an increase in hospital admissions.
Another study, conducted with 55 volunteers in the city of São Paulo, Brazil, who
measured NO2 levels individually for 7 days allowed the discovery of a considerable
number of people with ocular irritation when exposed to elevated levels of this
pollutant (NO2). NO2 was chosen as an indicator of the exposure to air pollution, and
in this research, the passive NO2 monitoring system was used because it is a simple
and efficient strategy that does not interfere with daily activities, allowing a good
sampling analysis for 3 weeks (Novaes et al. 2010).
Nitrogen oxides are usually found in exhaust gases from processes involving the
burning of fossil fuels, and among them, NO2 is considered as the highest environ-
mental and toxicological importance in the lower troposphere. NO2 is present in
significant concentrations in polluted atmospheres and is the most toxic (Novaes
et al. 2007; Fisher et al. 2007; Atkinson 2013).
The atmospheric levels of NO2, observed in urban outskirts, vary with the time of
day, the season, the proximity and the nature of the local sources of pollution, and
with the meteorological factors. In general, peak concentrations occur twice a day in
morning and evening hours and are attributed to emissions from road vehicle traffic
(Kuriyama et al. 1997; Sullivan and Pryor 2014), considering that in summer, NO2
concentrations are higher and more damaging (Ryley 2016).
NO2 is an oxidizing gas soluble in tissues and, due to its degree of tissue
solubility, reacts not only with the alveolar epithelium but also with the interstice
and endothelium of the pulmonary capillaries. This oxidative injury has been
enunciated as the main mechanism of pulmonary lesion formation. Most of the
inhaled NO2 is retained in the lungs and deposited, primarily, in the bronchi,
respiratory and terminal bronchioles, with small deposition in the alveoli. In this
way, NO2 can directly injure the lung by means of its oxidizing properties or,
indirectly, by increasing susceptibility to respiratory infections (Samet 1991). It is
of immense importance to highlight that exposure to NO2 is considered a sentinel
event in occupational health, being associated with exposure to NO2 the appearance
of acute bronchitis, pneumonia, and pulmonary edema (Mullan and Murth 1995;
Larsson et al. 2010).
Therefore, NO2 is considered a marker of pollutants derived from combustion
produced by vehicular emissions and other sources, such as biomass burning
(Novaes et al. 2010). When NO2 is absorbed by the smaller airways, at very high
concentrations (above 200 ppm), it is quite dangerous, causing lung injury, fatal
pulmonary edema, lung cancer, bronchopneumonia, and cardiovascular diseases
(Hamra et al. 2015). It causes impairment in mucociliary transport, decreasing
macrophage function and local immunity at lower concentrations (Wu 2014).
As NO2 is derived mainly from diesel, which is a widely used fuel in buses and
trucks, it is relevant to study the working conditions to which the drivers of these
means of transport are exposed. The health and working conditions of urban public
transport drivers can be considered as an essential element of dimensioning the
quality of life of urban centers since different environmental and social interaction
factors – among them, transit – contribute to the increase of stress and respiratory
diseases (Battiston et al. 2006).
The work of the urban public transport driver is directly related to the environ-
ment in which it is carried out. Unlike the people who perform their professional
activities indoors, this professional performs his work in a public environment, the
traffic. It does not, therefore, have a restricted and well-defined place to carry out its
tasks; on the contrary, it works outside the company’s gates, being subject to weather
conditions, such as climate, air pollution, and traffic conditions and pathways
(Battiston et al. 2006).
Air quality issues are increasingly among the most well-informed concerns of the
population, and more accurate responses are expected, but there are still insufficient
studies to prove the harm to individuals who are closest to sources of pollutant
emissions. In modern cities, where industries have moved away from more popu-
lated regions, buses become a predominant source of pollution. Therefore, exposure
to urban air pollution is associated with increased effects on the respiratory health of
the population.
Methods
This research consists of a literature review, developed based on studies on

the association between air pollution and respiratory health, more specifically,
the effects of NO2. Linde and Willich (2003) point out that a systematic review
is a form of research that is based on the literature as a data source, being
considered able to present conflicting and/or coincident results and to provide
support for future investigations (Hulley et al. 2003). The descriptors “air pollu-
tion,” “nitrogen dioxide,” “traffic or transport,” “indoor air quality,” and
“bus drivers” were used in the Medline and B-on databases in order to obtain
the articles analyzed. Reference lists of selected articles were also reviewed. The
research period included studies published until the month of July 2016. A
screening process was implemented based on article titles, abstracts, and
full texts, to identify suitable studies. First, the summaries of the articles found
were read, and therefore, the researches to be used in the analysis were selected.
The criterion of inclusion of articles was the use of those who analyzed
the association of NO2 with health effects. As exclusion criterion, it was adopted
to exclude those articles that analyzed only the association of meteorological
conditions with health problems.
Results
This topic presents the main results of studies on air pollution, NO2, and effects on
human health. The inclusion criteria were filled with 28 studies indexed in Medline
and B-on until July 2016. In total, 910 articles were found, using the descriptors in
910 potentially relevant publications,

initially identified.
745 articles excluded by title abstract

(slightly related to the subject)
165 articles obtained for detailed

evaluation
137 Articles excluded for little

relevance to the context of this review
28 articles fulfilled the inclusion

criteria
Fig. 1 Scheme for sorting articles of interest
the Medline and B-on databases, of which 165 were inclusion criteria and were
selected for the more detailed analysis (Fig. 1).
The study by Simoni et al. (2002) (ID 23) (Table 1) showed that there was a close
relationship between the levels of the 2 inside of 33 ppb in winter and there was an
increase in the occurrence of acute respiratory symptoms in nonsmoking adults. In
elevated levels of NO2, there was a prevalence of bronchitis and asthma. These effects
are combined with the duration of exposure to which individuals are submitted during
your daily routine. The same results were obtained (exposure indices) when the
subjects were exposed to a low dose of NO2 for an extended time (5 h) and when it
no longer reaches for a higher concentration of NO2 (50 ppb–101 μg/m3) for a shorter
time (1 h). Exposure to NO2 of 200 ppm (405 mg/m3) or higher places the life of the
individual in danger. In 50–100 ppm levels (101 mg/m3–203 mg/m3), NO2 damages
lung function and irritates the eyes, nose, and throat. The higher the concentration of
NO2, even in a brief period, the more damaging it will be for the pulmonary function.
Consider pulmonary function as an important indicator of respiratory health, and
with the increasing air pollution, the respiratory system is at risk, because the
gaseous pollutants and small particles in the air are absorbed through the nose and
mouth. In most of the studies, there is a greater concern for two pollutants, NO2 and
PM10, which are derived from sources related to traffic but are also raised in homes
with wood or gas stove and cigarette smoke. Both have been associated with
respiratory diseases, as well as to cardiovascular morbidity and mortality
(Brunekreef and Holgate 2002).
Table 1 List of articles that met the inclusion criteria published until July 2016
Variables evaluated
Air Study
ID Reference Diseases pollutants population
1 Behrentz et al. Asthma, decreased lung function, stress, PM, CO2, All
(2005) cardiovascular disease NO2
2 Briggs et al. Respiratory diseases NO2 All
(2016)
3 Brunekreef and Respiratory diseases PM, NO2 All
Holgate (2002)
4 Burr et al. (2004) Respiratory diseases, decreased lung PM2,5, All
function, asthma, rhinitis, conjunctivitis PM10, NO2
5 Cakmak et al. Respiratory diseases PM, CO2, All
(2016) NO2
6 Cheng et al. Respiratory syndromes and PM, CO2, Adults
(2006) inflammatory effects NO2
7 Chiu et al. Decreased lung function CO2, NO2 All
(2015)
8 Corfa et al. Respiratory and cardiovascular diseases PM, CO2, All
(2004) NO2
9 Crouse et al. Respiratory and cardiovascular diseases, PM2,5, O3, All
(2015) COPD, diabetes, lung cancer NO2
10 Fitz et al. (2003) Respiratory diseases and decreased lung PM2,5 e All
function NO2
11 Gauderman et al. Respiratory diseases and decreased lung PM, CO2, Children
(2000) function NO2
12 Gavinier and Cerebrovascular accident NO2 Adults
Nascimento >50 years
(2014) old
13 Huang et al. Reduction of FEV1 e PEF PM2,5, Young
(2016) NO2, BC e adults
CO
14 Hystad et al. Respiratory diseases and lung cancer NO2 All
(2013)
15 Lewné et al. Respiratory diseases NO2 Adults
(2006)
16 Lipfert and Premature mortality, asthma, decreased CO2, NO2 All
Wyzga (2008) lung function, stress, diseases
17 Liu et al. (2010) Respiratory diseases PM, CO2, All
NO2
18 Molle et al. Respiratory diseases PM2,5 e All
(2013) NO2
19 Mölter et al. Decreased FEV1, reduced lung volume PM10 e 3, 5, 8,
(2013) NO2 11 years
old
20 Negrisoli and Pneumonia NO2 All
Nascimento
(2013)
(continued)
Table 1 (continued)
Variables evaluated
Air Study
ID Reference Diseases pollutants population
21 Riediker et al. Fatigue, lack of concentration, and loss NO2 Adults
(2003) of cognitive ability
22 Rim et al. (2008) Decreased lung capacity NOx All
23 Simoni et al. Impairs lung function; irritates the eyes, NO2 Adults
(2002) nose, and throat
24 Solomon et al. Respiratory diseases and decreased lung NO2 All
(2001) function
25 Underhill et al. Cardiopulmonary diseases, asthma, PM2,5, BC, Adults
(2015) allergies, decreased lung function NO2
26 Vuković et al. Respiratory and cardiovascular diseases PM, NO2 All
(2016)
27 Wang et al. Respiratory diseases and decreased lung CO2, NO2 All
(2011) function
28 Zhang et al. Asthma, chronic obstructive pulmonary PM, CO2, All
(2016) disease (COPD). NO2
Abbreviations: NO2, nitrogen dioxide; CO2, carbon dioxide; NOx, nitrogen oxide; BC, black
carbon; PM, particulate matter; PM2,5, particulate matter of less than 2.5 μm in diameter; PM10,
particulate matter of less than 10 μm in diameter; COPD, chronic obstructive pulmonary disease;
FEV1, forced expiratory volume in 1 s; PEF, peak expiratory flow
Cheng et al. (2006) (ID 6) reported, in the cabins of buses, the air quality is
dependent on temperature, relative humidity, and concentrations of air contaminants;
these parameters can have a significant effect on the health and welfare of occupants,
as well as the temperature and humidity, and have a direct impact on the comfort.
The low air humidity has effects such as fatigue, headache, itchy skin and eyes, nose
bleeding, as well as impaired lung function. Indoor air contaminants during transport
include PM, CO2, and NO2. Fine particles are responsible for many respiratory
syndromes, and the ultra slim nanoparticles pose more threats to the occupants inside
because they can penetrate deeply into the respiratory system. The engine exhaust
nanoparticles can move from the lungs to the brain, consequently, causing blood
clotting and inflammatory effects (The Royal Society 2003; Dreher 2004).
NO2 is one of the main emissions of vehicles and roads; the concentration is very
high, reaching 212 ppb (101,429 μg/m3) (Riediker et al. 2003). This may result in
driver fatigue, lack of concentration, and loss of cognitive ability, reducing the
ability of the individual to operate the vehicle safely and generating a connection
between air quality and transportation risks.
Lipfert and Wyzga (2008) (ID 16) refer, in your research, which, traditionally, the
CO and NO2 are considered routinely more pollutants monitored by being identified
with the vehicular traffic, the largest emission source. They still reported that many
studies indicate an association between exposure to vehicular traffic and various
health complications, such as premature mortality, cardiac symptoms, lung cancer,
hypertension, impaired respiratory health, decreased lung function, a prevalence of
asthma, respiratory symptoms, stress, and, consequently, an increase in the number

of hospitalizations.
Gauderman et al. (2000) (ID 11), in a cohort of 3035 schoolchildren, for 4 years,
concluded that exposure to air pollution could lead to the reduction of maximum
lung function, which occurs at the beginning of adulthood and prevails to the
increased risk of chronic respiratory diseases.
Negrisoli and Nascimento (2013) (ID 20) developed a study on the relationship
between pollutants and hospitalizations for pneumonia in childhood. These authors
found strong correlations between pollutants (except for the ozone) and hospitaliza-
tions. They have identified an acute effect of nitrogen dioxide in hospitalizations for
pneumonia and concluded that the effect of the particulate matter presents itself later,
4 days after exposure.
Gavinier and Nascimento (2014) (ID 12), in Brazil, estimated the association
between pollution and hospitalizations for cerebrovascular accident (CVA) in indi-
viduals 50 years of age or older. In the study they have done, it was possible to
identify an association between NO2 and hospitalizations per CVA; these authors
also noted that the increase of 10 μg m–3 of NO2 represented an increase of four
percentage points in the risk of hospitalization.
In Asia, the group of Zhang et al. (2016) (ID 28) conducted a systematic review of
the literature, in December 2014, focusing on the search for diseases, pollutants,
types of hospitalization, and age groups of subjects. These researchers report that the
association between exposure to air pollution in the short term and morbidity due to
chronic obstructive pulmonary disease (COPD) and asthma has been observed in
several studies. By 26 works consulted, they concluded that the increase in the
period of the person’s exposure to air pollution results in greater risk for developing
COPD and asthma in the population, especially in the elderly and children. These,
for your time, tend to be more susceptible to the effects of air pollution on asthma
morbidity cases.
In another research, Chiu et al. (2015) (ID 7) suggest the increased frequency of
ventilation of bus cabins as a beneficial procedure to maintain the security of travel,
with the best quality for occupants. Bus cabins are specifically built for volatile organic
compounds (VOCs), which can be issued from the cabin furnishings, due to increase in
temperature by exposure to sunlight, being hazardous to the health of drivers who
normally spend prolonged periods inside the bus. Thus, the authors claim that the
increased temperature accelerates the spread of volatile organic compounds.
The group of Underhill et al. (2015) (ID 25), in their study, describes air pollution,
including fine particles (PM2.5) and black carbon (BC) NO2. According to research,
she is very well known by your impact as a cause of pulmonary heart diseases and
has been a source of concern in developing countries. They infer that vehicle traffic
may be related to poor air quality, due to the rapid expansion of metropolitan areas
and concomitant with the peaks of traffic and the use of pollution-generating fuels.
Understand that the burden of traffic-related exposure may be greater in underde-
veloped areas, due to the scarcity of actions in the regulation of pollution and air
quality control, as well as limitations in the availability of healthcare of the
population.
The increase in the external concentration NO2, due to the burning of fuel and the
high traffic intensity, smoking, poor natural ventilation, and heaters with pollutant
emissions, is associated with high concentrations of NO2 inside. Seasonal variation
and wind were also displayed to being related to the variation in levels inside. In a
cohort study, with about of 2,500,000 of Canadians, during 16 years of follow-up,
Crouse et al. (2015) (ID 9) investigated the association between mortality due to
environmental concentrations of PM2.5, O3, and NO2. These three pollutants were
positively associated with deaths from accidental causes, cardiometabolic care
diseases, diabetes, ischemic heart disease, lung cancer, respiratory diseases, and
chronic obstructive pulmonary disease. They found strong associations between
NO2 and mortality from lung cancer and respiratory diseases, which corroborate
the results of another case-control study (Hystad et al. 2013).
Burr et al. (2004) (ID 4) show that, in recent decades, there has been a growing
concern about possible adverse effects of the emission of pollution from vehicles
with internal combustion engines, in particular, diesel engines. One of the problems
generated, it is believed that this type of air pollution can cause or aggravate asthma
and other respiratory disorders. There are several epidemiological pieces of evidence
about the relationship between air pollution and respiratory diseases. Several studies
have suggested that respiratory disease (primarily asthma) or decreased lung func-
tion are associated near roads with high traffic of vehicles or exposure to pollutants
derived from vehicle engines.
Wang et al. (2011) (ID 27) did a study that assessed the public transport, and in the
case of buses, they discovered that these expand the pollutant emissions beyond
what is normally observed in taxis and private cars and that, moreover, such
concentrations increase sharply when the engine is accelerated. Few studies have
monitored the number of particles in real time, and a number, also, of very limited
studies focus on the evaluation of NO2 and CO in the underground transport in
stations with a mechanical ventilation system.
In the study conducted by Lewné et al. (2006) (ID 15), 121 were drivers. Of these,
39 were drivers, 42 bus drivers, and 40 truck drivers. The group reports the
occurrence of individual measurements at 2, using passive samplers during a day’s
work. Truck drivers had greater exposure NO2 (68 μg/m3), bus drivers had an
exhibition considered average (60 μg/m3), and taxi drivers showed a smaller exhi-
bition (48 μg/m3). Levels of NO2 were greater for bus drivers in the city than in the
suburbs. And using diesel or gasoline as a fuel for taxis has not been verified as an
influence on exposure to motorists, which indicates that the exposure of taxi drivers
depends on the engine exhaust and surrounding traffic.
Molle et al. (2013) (ID 18) evaluated for 10 days in 2010, in the city of Paris,
20 articulated buses that were in 32 different routes to determine the concentration of
pollutants. This parameter is still little known to the articulated buses but must be
considered, because the greater length of the bus can cause an increase in the
concentration of pollutants in the cabin. The researchers checked the concentrations
of PM2.5 and NO2 and measured the concentrations of these pollutants in three
positions on the bus (in front, middle, and rear), to assess the spatial distribution of
such compounds. Internal measurements were compared on the same days, with
measurements of concentrations of pollutants outdoors provided by air monitoring

network of the city of Paris. The product obtained was compared with that of an air
monitoring campaign in 2008, and the results found in 2010 showed that the
concentrations of NO2, inside the bus, were 1.5 to 3.5 times higher than the
concentration levels outside.
Other research shows studies with various measurements inside the bus to
represent the spatial distribution of pollutants (Solomon et al. 2001; Fitz et al.
2003). Behrentz et al. (2005), for example, found that the concentrations of pollut-
ants in the interior of the buses are higher compared to the outside air.
Rim et al. (2008) published a study that examined the quality of the air in Texas
school buses. In this case, the concentrations of nitrogen oxides (NOx) were 1.3 and
10 times greater than the concentration on the road. In all studies, the fuel used was
the diesel.
Liu et al. (2010) (ID 17), comparing situations where the windows were closed
with others in which they remained partially open, report that the concentrations of
pollutants were greater in the first case: with the windows closed. These elevated
levels of pollutants inside the bus can be a result of “auto pollution,” represented by
the air inside the cabin, from the engine of the bus.
Mölter et al. (2013) (ID 19) sought to study the long-term effects of exposure to
particles with aerodynamic diameter 10 μm (PM10) and NO2 on the specific airway
resistance and forced expiratory volume in 1 s (FEV1) before and after the use of a
bronchodilator. Spirometry was carried out in children ages 3, 5, 8, and 11 years old,
and they concluded that exposure to PM10 and NO2, throughout life, binds to the
decrease of FEV1 in relation to the percentage foreseen, both before and after the use
of a bronchodilator. Also, these findings led him to think that in the long term,
prolonged exposures to particles of PM10 and NO2 may be associated with a
reduction in lung volume in children of school age.
Vuković et al. (2016) (ID 26) reported that the transport sector represents the main
source of air pollution in urban areas, including PM and NO2, combined with other
toxic elements. These ingredients are often found in higher concentrations in areas
close to urban environments, such as main entries, crossroads, and bus stations. The
increase in air pollutants beyond the limit values has been associated with many
dangerous health effects, mainly respiratory and cardiovascular.
On New Zealand, an evaluation study was carried out of public transport on the
impact on environmental health, using a fast procedure. The incidence of diseases
and injuries was analyzed from the number of traffic accidents, air pollution, noise,
and physical activity. In total, road transport was responsible for 650 deaths in 2012
(2.1% annual mortality in the country): 308 due to traffic accidents, 283 caused by
air pollution, and 59 due to noise. Along with morbidity, these numbers represent a
total of 26,610 diseases lives. In general, the impacts of traffic-related air pollution
and noise are low compared with those recorded in other developed countries.
Traffic emissions are the main source of the NO2 in New Zealand (Briggs et al.
2016) (ID 2).
In Corfa et al.’s study (2004) (ID 8), scouting was carried out of the reach of air
pollution near the bus and railway stations. Early in the morning, they observed the
intense routine of many buses and trains, noting that the critical situation is deter-
mined, mostly due to the combination of three factors: cold engines, simultaneous
output of many buses and trains, and weather stable. They also compared the use of
diesel engine with CNG fuel, concluding that this last, with a minor emission of
pollutants, is more favorable to health.
In against the exposure to air pollution and the risk of respiratory
diseases, Cakmak et al. (2016) (ID 5), highlighting the social issues and
environmental differences found in many large cities, suggest that low-income
families, with lower level of education, have a higher risk of respiratory
diseases and decreased lung function, seen more closeness and contact with air
pollution.
In a crossover study, Huang et al. (2016) (ID 13) researched the situation of
40 young adults in a bus terminal, considering that this is where usually there is an
increase in emissions of pollutants and personal exposure to PM2.5, NO2, black
carbon (BC), and carbon monoxide (CO). Each participant underwent 2 h of
exposure in a bus terminal and, on another occasion, in a park. FEV1 occurred and
flowed peak expiratory (PEF) before, during, and after. The values of FEV1 and PEF
had significant reductions when evaluated in the bus terminal, as compared to the
time they were checked at the park. There was no acute reduction in lung function,
determined in healthy individuals who stayed for 2 h in the bus terminal, where
vehicles are diesel-powered. For instance, per 10 μg/m3 increment in PM2.5 was
associated with –0.15 % (95 % CI –0.28, –0.02 %) reduction in FEV1 during
exposure 2 h.
Conclusion
With this research, one can realize that, among the studies that have been developed,
there are a variety of diseases studied, noting that the effects of air pollution not only
affect the respiratory and circulatory system of the population exposed, but they can
be causes of risk for other problems, such as low birth weight, cancer incidence and
mortality from this disease, premature births, and heart disease. All studies included
in this review suggest that there is an association of air pollution with health
problems of populations examined, but the majority of the researches focus on
children under 5 years old and adults over 60 years old. There are few surveys of
individuals aged between 18 and 60 years old.
It was found, through this review, that despite technological advances, the current
pollution levels continue to be very harmful to health, becoming necessary to
conduct more studies that show the relationship between air pollution and its effects
on human health to ensure improved quality of information to be used by the
managers of companies that absorb workers exposed to situations such as those
described. It also stresses the importance of studies addressing the effects of the
interaction of people in the environment, as these extend the possibility of adopting
preventive measures capable of reducing environmental degradation and, conse-
quently, the adverse effects to people’s health.
Cross-References
▶ A New Method to Estimate the Instantaneous NOx Emissions from Road Traffic
▶ Air Pollution
▶ Integrated Evaluation of Quantitative Factors Related to the Environmental Qual-
ity Scenario
Acknowledgments This work was financed by Portuguese National Funds through FCT –
Fundação para a Ciência e Tecnologia (Portuguese Foundation for Science and Technology) as
part of the Project UID/Multi/04546/2013.
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Part VII
Environmental Treatment Technologies
Advanced Treatment Technologies
53
Manviri Rani and Uma Shanker
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1290
Pesticide Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1292
Organochlorine Pesticides (OC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1292
Organophosphate Pesticides (OP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1292
Substituted Urea Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1301
Carbamate Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1302
Biopesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1302
Miscellenous Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1302
Environmental Concern of Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1304
Need to Degrade/Removal of Pesticides from Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1305
Degradation Techniques of Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1306
Degradation of Pesticides Using Conventional Adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1307
Degradation of Pesticides Using Nano-adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1309
Degradation of OC Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1309
Degradation of OP Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1315
Degradation of SU Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1323
Degradation of Carbamate Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1324
Degradation of Miscellaneous Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1325
Utilization of Green Synthesized Nanomaterials in Remediation of Environment . . . . . . . . . . . 1326
Conclusions and Future Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1327
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1328
Abstract
Increasing population, rapid industrialization and extensive use of pesticides in
agriculture caused the discharge of pesticide residues into surface water. Among,
organochlorines (OCs) are critically noxious with half-lives of many years
M. Rani · U. Shanker (*)

Department of Chemistry, Dr B R Ambedkar National Institute of Technology,
Jalandhar, Punjab, India
e-mail: shankeru@nitj.ac.in

https://doi.org/10.1007/978-3-319-73645-7_33
1290 M. Rani and U. Shanker
followed by organophosphorus (OPs) and carbamates etc. Owing to carcinogenic

nature, most of OCs are banned worldwide and still existing in environment. Due
to great persistence, toxicity and potential to bioaccumulation, their complete
removal (including monitoring and regulatation) is highly imperative. In this
direction, traditional techniques such as microbial, photolysis and conventional-
adsorbents (commercial-activated-carbon, agricultural and natural-waste) were
highly employed. Of late, nanomaterials (including nanocomposites and nano-
biocomposite) with high surface-area come out as most economic, rapid and
effective photocatalyst under artificial and sun-light irradiation. TiO2 and Fe0
by itself or with oxidizing agents are being used frequently and open the oppor-
tunities for exploring other nanoparticles as well. Further, their modified, doped
or composites form showed improved properties via introduction of additional
energy levels or upsurge of surface area. However, metal oxides also found to
degrade OP pesticides by rapid reactive adsorption followed by cleavage of P-O
bond via SN2 mechanism. Present chapter familiarize readers with comprehen-
sive information on problem related to different types of pesticides (metabolites,
environmental concentration, and need for degradation) and their removal using
nanoparticles through adsorption, photocatalytic, redox and reactive degradation.
In addition, importance of green synthesized nanoparticles in degradation of
various organic-pollutants has been highlighted.
Keywords
Treatment technologies · Nano-adsorbents · Biopesticides · Organophosphorus ·
Degradation
Introduction
Currently, our environment is facing lots of challenges due to several types of pollution
which ultimately harming biota on earth. Therefore, in order to sustainable and better
life, it imperative to follow the rules of environmental management. In this direction,
advanced treatment technologies are being developed to eradicate such problems from
the environment. One of the greatest problems in developing countries is the pollution
caused by the unauthorized loading of pesticides, deliberately expended to preserve the
agricultural produce. A small amount (~10%) of applied pesticides are adsorbed by
target and abundant part dispersed off into to air, soil and water and impair their quality
depending on their persistence (Cahill et al. 2011). They are highly toxic, and suspected
carcinogens causing threats to environmental contamination with their alarming levels
(Rehana et al. 1995; Ahmed et al. 2011). In addition, pesticides are the known
homicidal and suicidal agents because of their easy availability (Gunnell et al. 2007;
Gannur et al. 2008). Therefore, they are listed as Priority Hazardous Substances by the
Water Framework Directive of the European Commission. Industries, mining, urban
activities and agricultural surface runoff are the potential sources to wastewater pollu-
tion, a highly recognized problem to developing countries (Malato et al. 2000; Varma
and Varma 2005). Because of strict regulations implemented, application of these
persistent organic pollutants (POPs) has been reduced but still detected in natural
53 Advanced Treatment Technologies 1291
Fig. 1 Biological transfer of pesticide to man
water (Kaushik et al. 2010; Navarro et al. 2010). The pictorial representation of the
biological transfer of pesticides to man has been depicted in Fig. 1.
In 2014, pesticides are abundantly used with sales amounted to close to
400,000 tonnes in Europe followed by Asia. Spain (19.9%), France (19.0%), Italy
(16.2%), Germany (11.6%) and Poland (5.9%) were the Member States in which the
highest quantities of pesticides were sold, and together they made up 72.7% of the
EU-28’s pesticide sales (EC 2016). The worldwide consumption of pesticides in kg
ha-1 followed the order: Taiwan (17) [China (13) [Japan (12) [USA (7) and Korea
(7) [France (5) and UK (5) (Singh et al. 2014). In Asia, China and India (100,000 MT)
are the chief manufacture of pesticides (Annual Report Govt. of India 2015). In India,
OCs and OPs are the most important pollutants while atrazine (57.39 million pounds)
is a widely used pesticide especially in the developed countries (Zhang et al. 2011).
Due to toxicity and prevalence of pesticides and their metabolites, there is an

urgent need to detect and develop low-cost and/or easy-to-handle, green and effec-
tive treatment processes to treat those perilous contaminants (Pitarch et al. 2010).
The use of various low-cost conventional adsorbents (Ahmed et al. 2010), advanced
oxidation processes (AOPs) (Burrows et al. 2002) and heterogeneous photocatalysts
of OP pesticides by aqueous TiO2 suspension using artificial and solar light are
reported (Konstantinou and Albanis 2003; Devipriya and Yesodharan 2005; Sud and
Kaur 2012). Moreover, the use of technologies like nanoparticles should be pro-
moted as being efficient, cheap and environmental friendly. For removing more or
less whole OCs, TiO2 and Fe0 (unique photocatalytic and redox properties) are used
(Rani et al. 2017a). Hence, in view of these shortcomings, present chapter deals
exclusively with the remediation of traditional and new emerging pesticides by
different nanomaterials or their modified forms operated through adsorption, reactive
adsorption (SN2 reaction) and photocatalytic mechanism.
The possible degradation pathways of various classes of pesticides and their
by-products have been widely discussed and evaluated. In addition, role of green
synthesized nanoparticles in degradation of various organic pollutants have been
highlighted. Biopesticides are biodegradable and least toxic, therefore, we have
confined the discussion only to OCs, OPs, carbamates and Substituted ureas (SU).
Tables 1, 2, 3, and 4 describes the physiochemical properties of various OCs, OPs,
Carbamates, SU and pyrethroids, respectively.
Pesticide Classification
The classification of pesticides either on the basis of target use (fungicide, insecti-
cide, and herbicide) or their chemical composition (Table 2) can provide useful
information about the pesticide chemistry, their action on the target, etc.
Organochlorine Pesticides (OC)
A group of persistent organic pollutants (POPs) and chlorinated ethane derivatives,

such as DDT and methoxychlor (Fig. 2) have been widely used. Due to high
persistence and slow degradation in environment, most of OCs are banned for
utilization but their illegal use continues particularly in the developing countries.
Several OCs were detected in water, human breast milk and foodstuffs (Sudaryanto
et al. 2006; Shoiful et al. 2013; Zhenwu et al. 2013; Kafilzadeh 2015).
Organophosphate Pesticides (OP)
The derivatives of phosphoric acid, are persisting in many environmental segments

and generally more toxic (Jokanovic 2001; Costa 2006, (Fig. 3). After the ban on
OCs, the OPs are getting more popular and being used worldwide. Moreover, due to
Table 1 Physiochemical properties of various OC pesticides
53
Water
Mol. solubility Log Vapor pressure log Koc Brand
S. no Compound Cas no wt (mg/L) Kow 20–25 C (mmHg) t1/2 (days) (cm3/g) Status (banned) name
1 Aldrin 309-00-2 364.9 0.19 6.5 1.2 104 266 5.4 South East Asia Aldrimul
2 α ()-BHC 319-84-6 290.8 100 3.8 4.5 105 9490 3.6 U. S. Alpha-
HCH
β-BHC 319-85-7 290.8 50 3.78 3.6 106 6.3 3.6 U. S. –
γ-BHC 58-89-9 290.8 N.S 3.72 4.2 105 1 3.6 U. S. Bio-well,
(Lindane) G-well
δ-BHC 319-86-8 290.8 100 4.14 3.5 105 0.7–0.9 3.8 South East Asia –
3 Dieldrin 60-57-1 380.9 0.11 5.4 5.9 105 369 6.7 South East Asia Deldrite
4 Endosulfan 959-98-8 406.9 0.32 4.7 1.2 Pa 50 4.0 India Endocel
5 Endrin 72-20-8 380.9 N.S 3.2–5.3 2.0 107 2190 5.2 South East Asia Hexadrin
6 Heptachlor 76-44-8 373.3 0.18 5.44 3 104 250 5.3 U.S. Drinox
7 Methoxychlor 72-43-5 345.6 0.04 5.08 4.2 105 <180 4.9 Use Chemform
8 p,p0 -DDD 72-54-8 320.1 0.09 6.02 1.3 106 3800 5.2 Banned –
9 p,p0 -DDE 72-55-9 318.0 0.12 6.51 6 106 2064 4.7 Banned –
10 p,p0 -DDT 50-29-3 354.5 0.025 6.91 1.6 106 1460–10,950 5.2 U. S., Canada, Dedelo,
Singapore Anofex
11 Pentachloro- 87-86-5 266.3 2000 5.15 1.7 104 1–3 3.7 Restricted in U. S. Dowicide
phenol EC-7
12 Piperonyl- 51-03-6 338.4 <100 4.75 1.3 102 73 3.2 Use Butacide
butoxide
13 Toxaphene 8001-35-2 414.0 3 4.77 0.4 0.5 3–5 Restricted Alltex,
(Argentina and Allotex
Columbia)
14 Quintozene 82-68-8 250.3 0.551 5.17 0.22 Pa 1.8 4.8 Restricted Pentagen
15 Chlordane 57-74-9 409.8 1 6.16 1 105 37–3500 3.5–4.6 South East Asia Belt
16 Dicofol 115-32-2 370.5 0.8 4.28 0.18 mP 16 4.1 Norway, Hilfol,
Netherlands Acarin
1293
1294
Table 2 Physiochemical properties of various OP pesticides; w week, h hour and s second

Water
Mol. Solubility Vapor pressure t1/2 Koc Status
S. no Compound Cas no wt (mgL1) Log kow (20–25 C) (days) (cm3/g) (banned) Brand names
1 Acephate 30560-19-1 183.0 650 1.9 2.3 104 13 0.48 – –
2 Azinophos 86-50-0 317.3 44 2.7 1.8 104 52 1465 Europe Orthene,
methyl Asataf
3 Chlorfen 470-90-6 359.6 145 3.8 1 103 1 2.68 Europe –
Vinophos
4 Chloropyrifos 2921-88-2 350.6 1.4 4.96 2.7 103 94 4981 Europe –
5 Diazinon 333-41-5 304.3 60 3.3 1.2 102 23 272 Singapore –
6 Dichlorvos 62-73-7 220.9 18,000 1.9 2.1 <1 28–152 Banned –
7 Dimethoate, 000060-51-5 229.3 23 0.8 1.1 103 7 20 India –
8 Ethion 000563-12-2 384.5 0.195 5.07 1.5 106 7–8 w 15,435 Banned Actithion
9 Ethylparathion 350820-04-1 291.3 11 3.83 8.9 104 14 5000 US Aileron
10 Fenamiphos 22224-92-6 303.3 700 3.3 0.12 103 16 267 Use Nemacur
11 Fenitrothion 122-14-5 277.2 30 3.5 18 103 50 h 440 Restricted Sumithion
12 Fenthion 55-38-9 325.3 4.2 4.84 7.4 104 34 1500 Restricted Pentox
13 Glyphosate 1071-83-6 169.1 0.12 3.3 1.3 104 3–130 24,000 Netherlands Dow
Glyphosphate
360
14 Malathion 000121-75-5 330.4 145 2.8 2.26 104 1 1800 Restricted Karbofos
15 Methamidophos 10265-92-6 141.1 90,000 0.8 2.3 103 >2.6 1.7 China, US Tamaron,
monitor
16 Mevinphos 26718-65-0 224.1 Soluble 0.13 1.7 102 3 44 Banned Phosdrin,
Phosfene
M. Rani and U. Shanker
53
17 Monochrotophos 006923-22-4 223.2 Soluble 0.2 2.9 104 30 1 India, China –

18 Oxydemeton 301-12-2 246.3 Soluble 0.74 3.8 105 3.2 – General use Metasysto-R
methyl
19 Parathion methyl 298-00-0 263.2 55 3 0.2 103 18.5 236 Indonesia, Devithion
Sri Lanka
20 Phorate 000298-02-2 260.4 50 3.56–3.9 8.5 102 60 1000 New Zealand Thimet
21 Pirimiphos- 29232-93-7 305.3 9.9 10 2 103 10 1000 General use Actellic
methyl
22 Paraxon 311-45-5 275.2 3640 1.98 1 17.7 s 48 Restricted Metaphos
23 Parathion 56-38-2 291.3 24 3.83 3.78 105 1–30 5000 Restricted Alkron
24 Profenophos 041198-08-7 373.6 28 4.68 1.24 104 8 2000 India Curacron
25 Terbufos 13071-79-9 288.4 2.3 5 3.46 102 5 5000 Banned Aragran
26 Tetrachlor- 22248-79-9 365.9 11 ND 5.6 106 2 900 Banned Rabon

vinphos
27 Triazophos 24017-47-8 313.3 30 3.3 0.39 103 9.059 355 Banned Hostathion
28 Trichlorfon 52-68-6 257.4 120,000 0.43 2.26 104 29 29 Brazil Chlorfos
29 Quinalphos 013593-03-8 298.3 22 4.44 2.1 104 6 1500 India Krush EC
1295
1296
Table 3 Physiochemical properties of various carbamate pesticides

Water solubility Log Vapor pressure t1/2 Trade
S. no Name Cas no M. wt (mgL1) Kow (mmHg) (days) Koc Status name
1 Aldicarb 116-06-3 190.3 60,000 1.13 – 30 30 EPA ban Temik
2 Aminocarb 2104-64-5 208.3 0.4 5.15 1,88 106 30 3–4000 – –
3 BPMC 3766-81-2 207.6 660 4.24 1.6 mPa 191–200 – – Lehar,
osbac
4 Bendiocarb 22781-23-3 223.2 40 1.7 3.5 105 >1–4 w 27–573 Restricted Ficam
5 Carbaryl 63-25-2 201.5 40 4.7 1.17 106 10 300 – Sevin
6 Carbofuran 1563-66-2 221.5 700 5.4 3.4 106 3–60 – – Furadan
7 Carbanolate 671-04-5 213.7 202 2.65 0.000922 – – Obsolete –
8 Dimetilan 644-64-4 240.3 8140 0.27 9.7 105 72 – – Dimetan
9 Formetanate 22259-30-9 257.7 500,000 – 3.6 103 100 1,000,000 – Carzol
10 Methiocarb 2032-65-7 225.3 24 2.92 5 105 30 3000 Use Mesurol
11 Methomyl 16752-77-5 162.2 58,000 2.38 5 105 33 160 Restricted Lannate
12 Mexacarbate 315-18-4 222.3 100 2.86 0.1 at 139 C 10 300 Use Zectran
13 Oxamyl 23135-22-0 219.3 280,000 2.38 2.3 104 4 25 Restricted Vydate
14 Pirimicarb 23103-98-2 238.3 2700 – 4.0 mPa 10 60 Use Pirimor
15 Promecarb 2631-37-0 207.3 91 3.1 0.00003 20 200 Use Carbamult
53
16 Propoxur 114-26-1 209.2 1800 1.45 1.3 Pa at 130 C 30 30 Use Baygon

17 XMC 2655-14-3 179.2 – 2.23 – 12.8 389 Use Meobal
18 Xylylcarb 10/7/2425 179.2 580 – 0 mPa – – – S-1046
19 Thiram 137-26-8 240.4 30 1.73 >7.5 106 15 383 Use Arasan
20 Trimethacarb 12407-86-2 193.2 58 – 5.1 105 20 400 Use Broot
21 Thiodicarb 59669-26-0 354.5 19 – 7 105 7 350 – Larvin
22 Asulam 337-71-1 252.2 550,000 0.3 0.005 mPa 7 40 Use Asulox
23 Barban 101-27-9 258 11 3.41 5 105 5 1000 Obsolete Carbyne
24 Carbetamide 16118-49-3 236.3 Soluble – 760 – – – Ertavas
25 Desmedipham 13684-56-5 300.3 8 3.39 400 mPa 30 1500 Use Betanex
26 Phenme-dipham 13684-63-4 534.6 4.7 3.59 1 1011 30 2400 Use Betanal
27 Propham 60364-26-3 179.2 250 2.6 – 10 200 Use Chem-hoe

28 Chlorpropham 101-21-3 213.7 89 3.51 7.5 106 30 400 Use Beet-
Kleen
29 Benomyl 17804-35-2 290.3 2 1.36 <5 106 240 1900 Use Benlate
30 Carbendazim 10605-21-7 191.2 8 1.52 9 10–5 Pa 120 400 Use Delsene
31 Thiophanatemethyl 2356-40-58 342.4 3.5 1.4 <1.3 102 pa 10 1830 Use Alban
1297
Table 4 Physiochemical properties of various SU and pyrethroids pesticides
1298
Water Vapor
Mol. solubility Log pressure t1/2
Group Name Cas no weight (mgL1) kow (mmHg) (days) Koc Status Trade name
SU Bensulfuron methyl 83055-99-6 410.4 120 1.8 2.8 1012 5 370 General use Londax
Chlorimuron ethyl 90982-32-4 414.8 1200 2.5 4 1012 40 110 General use DPX-F6025
Chlorsulfuron 64902-72-3 357.8 7000 0.74 4.6 106 40 40 General use Sinon angle
750 WG
Linuron 330-55-2 249.1 75 3.2 1.5 105 60 400 General use Afalon
Metsulfuron methyl 74223-64-6 381.4 9500 1.7 2.5 1012 30 35 Commercial use Stinger
Primisulfuronmethyl 86209-51-0 468.3 70 0.06 <5 103 30 50 General use Beacon
Prosulfuron 94125-34-5 419.4 2.102 3.02 1.3 103 16 23 General use Peak
Pyrazosulfuron ethyl 93697-74-6 414.4 – 1.3 – – – Commercial use Pendimethalin
Sulfamethazine 57-68-1 278.3 1500 0.19 8.6 109 18 191 General use Sulpha
methazine
Thifensulfuron 79277-67-1 387.4 2400 1.56 1.3 1010 12 45 General use Harmony
methyl
Triasulfuron methyl 82097-50-5 401.8 – – – – – – Logran
Tribenuron methyl 101200-48-0 395.4 280 0.3 4 1010 12 46 General use Express
Pyreth- Bifenthion 82657-04-3 422.9 0.004 6 1.8 107 30 100,000 Restricted Talstar
roids Cypermethtrin 52315-07-8 416.3 Insoluble 6.6 4 108 160,000 Restricted Ammo
Deltamethrin 52918-63-5 505.2 <0.1 6.2 1.5 108 31 10,240,000 General use Butofin
Esfenvalerate 66230-44-04 419.9 0.002 7.2 0.067 mPA 35 5300 General use Ectrin
Fenpropathrin 39515-41-8 349.4 0.33 6 5.5 106 5 5000 General use Danitol
Fenvalerate 51630-68-0 419.9 0.002 6.2 1.5 10–9 35 5300 General use Ectrin
Permethrin 52645-53-1 391.3 0.006 2.88 4.5 10- 30 100,000 Restricted Ambush
6 mbar
Pyriminobac-methyl 136191-56-5 361.3 0.175 2.7 3.5 10- – 5–20 Caution in use Saturn
2 mPa
Resmethrin 10453-86-8 338.4 0.01 5.43 2.58 30 100,000 Restricted use Chrysron
Fig. 2 Structures of various organochlorine pesticides
high polarity and dissolution capacity OPs may easily enter into the soil and transfer
to other places (Costa 2006, Kolpin et al. 1998). The OP pesticides, no doubt are
effective, but they cannot be rated as innocuous or less toxic. They inhibit acetyl-
cholinesterase enzyme which results into the accumulation of acetylcholine in nerve
tissue. The nerve starts firing in an uncontrolled manner and as a result organism
Fig. 3 Structures of various organophosphate pesticides

(pest/insect) is quickly killed (Ecobichon 1991; Padilla et al. 1994). Their use as
intentional or unintentional poisoning agent has become a common practice (Goel
et al. 1998; Das 2007; Gannur et al. 2008; Mehrpour et al. 2008).
Substituted Urea Compounds
Urea type pesticides constitute of a urea bridge substituted by triazine,

benzothiazole, sulfonyl, phenyl, alkyl or other moieties (Fig. 4). These herbicides
O N
O S O HN N Cl
O N O
HN O Cl
N N O O O N
OO S O N
N S
O N N N
O H H O
O
Bensulfuron-methyl Chlorimuron-ethyl Chlorsulfuron
O
N F
O O
HN O OCH3 O F
C OCH3 O
O O N
H O O N
S N C NH N F
S
Cl O N O N N N O
CH3 H H F
Cl
Linuron Metsulfuron-methyl Primisulfuron-methyl
F
F
O
F
O O N
O O
S
O O N N N O O N N N
H
S N S
O N N N O N N N O H2N
H H O H H
Prosulfuron Pyrazosulfuron-ethyl Sulfamethazine
O
Cl N N
O CH2
O CH2 N N
S H3C
O O N O O O
N N O HN
S C
N N N N N N S OO S O
O O H H
H H N O
H3C O O
Thifensulfuron-methyl Triasulfuron-methyl Tribenuron-methyl
Fig. 4 Structures of various substituted urea pesticides

(Fig. 4) with high selectivity and lowest persistence (t1/2 = few days to weeks;
ethametsulfuron-methyl 13–67 days) are used in low dose (10–40 g a.i. ha1).
They contain free imino hydrogen which forms H-bond to inhibit the acetolactate
synthase enzyme (Wang et al. 2010). Diuron could decrease photosynthesis
efficiency even at concentration of 1.5 μg L1 (Ricart et al. 2010). Lower persis-
tence does not necessarily correspond to lower toxicity; since many new species
might get formed which are potentially more toxic and stable than the precursors
(Bottaro et al. 2008).
Carbamate Pesticides
The economic conditions prevailing in developing countries dictate the use of

cheaper broad spectrum carbamate pesticides, derivatives of carbamic acid (Fig. 5)
and are used in different situations. Their toxicity to mammals and their persistence
in the environment may vary from low to medium. They also inhibit the vital
enzymes like cholinesterase (Gruber and Munn 1998; Lazartigues et al. 1998;
Masuda and Kawamura 2003). Some commonly used carbamates are carbofuran,
carbaryl, thiram and mancozeb. Diazinon carbamate is one of the most commonly
detected insecticides in air, rain and fog (Pesticide news 2000). Carbaryl
caused cardiac effects in zebrafish (Danio rerio) embryos (Lin et al. 2005)
and reproductive toxicity of carbofuran and mancozeb was reported for female rats
after a chronic exposure (Baligar and Kaliwal 2001, 2002). The metabolites of
carbamates e.g. dimethyl dithiocarbamate and carbon disulfideare also reported to
have a toxicological concern (Chapalamadugu and Chaudhry 1992).
Biopesticides
The extensive use of the OCs, POs and other category of chemical pesticides
has caused into several environmental issues and there is an emphasis to develop
safer alternatives. Biopesticides are the derivatives of plants (pyrethroids) and
microorganisms (derived from fungi, bacteria or virus). Several biopesticides have
been used as plant protectants, such as dipel (Bacillus thuringiensis, bacteria), bicon
(Paecillomyceslilacimis, fungi) and spod-X (Insect virus) (Isman 1994, 1997) and a
number of others are under development, such as pyrethrum (Chrysanthemum
cineraiaefolium), neem (Azadirachta indica), nicotine (Nicotiana sp.), rhyania (Der-
ris lonchocarpus). A large scale use of these biopesticides by a common farmer is
still awaited due to the high cost restrictions and their availability.
Miscellenous Pesticides
There are emerging concern of currently used pesticide belonging to various groups
such as neonicotinoid (insecticides), pyridazinone and triazine (herbicide) etc.
Fig. 5 Structures of various carbamate pesticides
Neonicotinoids pesticides accounted for about 24% of the total world insecticides
market in 2007 (Jeschke et al. 2011) and can be divided into three main classes:
chloropyridinyl compounds (imidacloprid, nitenpyram, acetamiprid, thiacloprid),
chlorothiazolyl compounds (thiamethoxam, clothianidine) and tetrahydrofuryl com-

pounds (dinotefuran). Low soil sorption and high leaching capability of Imidacloprid
and Thiamethoxam make them potential contaminants of surface and underground
waters (Muccio et al. 2006). Degradation of chloridazon that caused many deceases
is rarely reported (Buttiglieri et al. 2009). Chloridazon and metribuzin possess high
mobility in soil and thus leaches and pollute surface and groundwater (Perez et al.
2010). Atrazine is a member of the triazine herbicide family intensively used to
control weeds for crop production.
Environmental Concern of Pesticides
Pesticides are inherently toxic i.e., mutagenic, carcinogenic and tumorogenic due to
this they have attracted attention around the globe (Kuroda et al. 1992; de Flora et al.
1993; Rehana et al. 1995). Their accidental use, spillage or misuse damaged practi-
cally all the segments of the environment (Broughton 2005; Baker et al. 1978). Some
important pesticide related accidents has been listed in Table 5 (Rani 2012).
Due to poverty and failure in life, annually about three million people
consume these cheap chemicals intentionally resulting into 220,000 deaths (WHO
1990). Most of them (99%) are from developing countries like Asia including
India (Gunnell et al. 2007). In India, <51% of food products are contaminated
with pesticide residues (Gupta 2004). In USA, the milk available from various
sources was reported to be contaminated with pesticides (Calabrese 1982).
The widely used OC and OP are persistent i.e., resistant to biodegradable, or are
degraded very slowly and form complex (Nagata et al. 1999). Some of them are
banned but still present in environment because of longer half-lives or recent use.
Recently in 2015, DDE was detected in Lake Tashk, Iran at the mean concentrations
of 0.075 ppb (water), 8.750 ppb (sediment) and 4.446 ppb (fish) (Kafilzadeh 2015).
Elevated concentrations of chlordane compounds were detected from Australian
seafoods (Kannan et al. 1997). Very high concentrations of HCHs and DDTs were
reported in 1978, ranging from 63 to 1400 ng/g (wet weight) in Chinese foodstuffs
(Li et al. 1998). The production of DDTs and HCHs was banned in 1983 in China
(Wolfe et al. 1984), but their concentrations in foodstuffs found relatively high in
1990 much greater than those in urbanized countries (Chen and Gao 1993). Presence
of atrazine in several rivers of Europe has been reported by Konstantinou et al.
(2006). It is found to have reproductive toxicity to the fish (Papoulias et al. 2014).
Studies revealed that rivers like Ebro (Spain), Marne (France), Po (Italy), Tejo
(Portugal), Humber (UK), Scheldt (Netherlands), and Elbe river (Belgium) were
all contaminated by the OC pesticides (Zhou et al. 2001). In India, worrying levels of
pesticides have been reported in water, air, soil as well as in food stuffs and
biological materials (Viswanathan 1985). Most of these pesticides have found
toxic, mutagenic, carcinogenic and tumorogenic (de Flora et al. 1993; Kuroda
et al. 1992; Rehana et al. 1995). India is still one of the highest lindane contaminated
country in the world in spite of its reduced production (Li 1999; Ramakrishna and
Philip 2008). From the above discussion it is clear that irregular use of pesticide is
harmful to human beings and environment.
Table 5 Some important pesticide related accidents

Pesticide Place Year Causes Reference
Parathion Kerala, 1958 Contaminated food due to Rani
India leakage (2012)
Bombay, 1962 Inhalation in
India manufacturing plant
HCH Bombay, 1963 Contaminated rice
India
Endrin Bombay, 1964 Contaminated food
India
HCH Bombay, 1963 Contaminated rice
India
Endrin Bombay, 1964 Contaminated food
India
DDT Punjab, 1965 Contaminated chutney
India
Diazinon Pune, India 1968 Contaminated food
HCH UP, India 1976 Mixed with wheat
Endrin Karnataka, 1977 Contaminated crabs in
India rice field
Aluminum phosphide Rajasthan, 1983 Contaminated food grain
India
Methyl isocyanate Bhopal, 1984 Storage tank leakage
India
Cartap hydrochloride Tamil 1988 Factory workers
Nadu,
India
Endosulfan Kerala, 1997 Contamination due to
India aerial spray of endosulfan
Phorate Kerala, 2001 Spray drift from banana
India field
Endosulfan MP, India 2002 Contaminated wheat flour
2,3,7,8- Seveso, 1976 Air pollution due to De
tetrachlorobenzo-10- Italy poisonous gas of TCDD (2010)
dioxin (TCDD)
Paraquat Japan 1985 Mass-poisoning Nagami
Sarin 1995 (2010)
Pesticides USA 1968–1978 Contaminated food Laseter
(1978)
Need to Degrade/Removal of Pesticides from Water
Pesticides, particularly OCs and OPs are carcinogenic with high persistence in soil
and water and lesser degradation i.e., high stability towards heat, light, oxidizing
agents and microbial attack (Cortes and Hites 2000; Barcelo and Hennion 2003). For
example, half-life of γ-HCH was calculated to be 191 days (Kafilzadeh 2015),
whereas, the average half-life of γ-HCH and α-HCH around the Great Lakes region
ranged from about 3 to 4 years (Cortes and Hites 2000). It was reported that even less
than 1 ppm of pesticide concentration makes the ground- and surface waters as well
as effluents polluted (Gilliom 2001). Their high use and subsequent discharge
resulted in widespread contamination and bioaccumulation Several OCs were
detected in water (0.068–0.098 ppb), foodstuffs (0.027–0.045 ppb) and human breast
milk (Gilliom 2001; Sudaryanto et al. 2006; Shoiful et al. 2013; Zhenwu et al. 2013).
Sometimes, their metabolites are more toxic than parent compounds such as oxons
(Gupta et al. 2011, 2012a, b, c). Matsumura (1985) has suggested that the metabolic
products of OP pesticides are more toxic to plants and animals than the parent
compound. However, Vasilic et al. (1992) observed that the presence of their diester
metabolites in human serum and urine is an indicator of exposure rather than of a
toxic effect. Studies on the suicidal/ homicidal effects of OP pesticides poisoning are
of immense importance in the field of toxicology (Teixeira et al. 2004). The
by-products of DDT degradation, i.e. DDE and DDD are very toxic and even dieldrin
is the toxic by-product of aldrin (Tian et al. 2009; Kusvuran and Erbatur 2004).
Therefore, in 1997, the European Directive 91/414/EEC and its subsequent amend-
ments established that, before a new pesticide is launched in the market, its complete
environmental data must be provided (Barcelo and Hennion 1997). Owing to these
adverse effects of extensive use of pesticides as well as their toxic metabolites
formedin environmental bodies, their degradation is highly imperative (Nemerow
and Dasgupta 1991; Tchobanoglous and Franklin 1991; Ali and Aboul-Enein 2004).
Degradation Techniques of Pesticides
Several methods such as bioremediation, fluid extraction (Lagadec et al. 2000), solid
phase extraction (Masselon et al. 1996), adsorption (Danish et al. 2010), aerobic
degradation (Rajashekara et al. 2007), electrochemical and biological oxidation,
advanced oxidation processes including homogeneous and heterogeneous photo-
catalysis (Maldonado et al. 2006; Aungpradit et al. 2007; Martin et al. 2008) and
nanofiltration membranes (Ahmad et al. 2008).
Adsorption was found one of the most simple, efficient, cost effective and flexible
method (Foo and Hameed 2010). However, this technique does not lead to the
complete removal of pesticide and further chemical treatments are needed to
minerlization of pesticides. This could be possible by use of reactive nanomaterials
(such as reactive sorbents” or “stoichiometric reagents, semiconductors, zero-valent
metals, nanocomposites etc.) which take part in either hydrolysis or elimination,
photocatalysis, reduction, or oxidation reactions (Yang et al. 1992; Tiwari et al.
2008). Similar to hydrolytic reactions in aqueous solutions (Meng et al. 2011), the
possible reaction pathway of reactive sorbent involves the nucleophilic attack on the
phosphorus atom with liberation of leaving group via transition state. They have
high porosity, high surface area (>100 m2/g), unique nanostructure with unusual
crystal planes and a large number of edges corners and point defects acted as active
sites for rapid reactive adsorption (Klabunde et al. 1996; Winter et al. 2009).
Secondly, advanced oxidation processes (AOPs) involving the generation of highly
reactive free radicals species. These active radicals reacted with organic contami-
nants to convert into mineral salts and nontoxic byproducts (Anipsitakis and
Dionysiou 2003; Bandala et al. 2007). Free radicals works by hydrogen abstraction
or by electrophilic addition to double bonds present in contaminant to generate free
radicals (R•) which will form peroxyradicals and start oxidative degradation chain
reactions that finally lead to mineralization of the organics (RH+HO• (or SO4•) to
HR•+H2O) (Blanco 2003). Homogeneous photocatalysis involves use of several
oxidizing agents such as H2O2, O3, Fenton reagent and NaOCl singly or with
exposure of light (UV, visible or solar) (Bolton and Cater 1994). Contrary, hetero-
geneous photocatalysis operates with use of oxides (TiO2, ZnO, ZrO2, etc) and
sulphides (ZnS, FeS etc.) of metals as semiconductor catalyst in the presence of
UV/solar radiation (Robertson 1996) where semiconductor is exposed to a light
source of particular wavelength, the electrons from valence band are promoted to the
conduction band leaving the positive holes. The generated electron-hole pairs moves
to the surface of semiconductor and degrades the organic pollutants into nontoxic
products (Yasmina et al. 2014; Lavand and Malghe 2015). Nanomaterials such as
TiO2 and ZnO are an excellent examples of such semiconductors photocatalyst with
high adsorbing capacity, advanced characteristics (size, morphology, high surface
area and other size dependent properties) and appears as the most emerging destruc-
tive technology. Because of inherent destructive nature, they does not involve mass
transfer and the process can be carried out under ambient conditions (atmospheric
oxygen is used as oxidant). Schematic diagram for photocatalytic pesticides degra-
dation using TiO2 nanoparticles is shown by Fig. 6.
Since early 1990s, environmental applications of metallic iron (moderate reduc-
ing reagent) or zero-valent iron (Fe0) have been widely adopted by several users and
government agencies, mainly because of low costs and nontoxicity by the use of iron
(Gillham and O’Hannesin 1994; Orth and Gillham 1996; O’Hannesin and Gillham
1998). Working of Fe0 involves the electrochemical/corrosion reactions where iron
got oxidized from exposure to oxygen and water. Contaminants freely accept the
electrons from iron oxidation and reduced to in according to their stoichiometry.
Nanocomposites and nanobiocomposites based on metallic nanoparticles have
witnessed an exponential growth in the field of nanotechnology due to improved
thermal stability, biocompatibility, optical, catalytic, mechanical, magnetic, thermal,
barrier and other properties. They are prepared by reinforcing the nanofiller into the
material such as Ceramic (e.g. Al2O3/SiO3, SiO2/Ni), Metal (e.g. Co/Cr, Fe/MgO)
and Polymer (e.g. polyester/TiO2) or biopolymer (Averous and Pollet 2012; Rhim
et al. 2013).
Degradation of Pesticides Using Conventional Adsorbents
Conventional adsorbents are the materials having particle size bigger than nanometer
and they were used in bulk. Reviews on removal of pesticides from water and
wastewater by different adsorbents including carbonaceous materials has been
presented (Kyriakopoulos and Doulia 2006; Ahmed et al. 2010; Foo and Hameed
Fig. 6 Schematic diagram for photocatalytic pesticides degradation using TiO2 nanoparticles
2010). These review indicated that activated carbon (AC) is extensively used in view
of its larger surface area and porosity (Matsui et al. 2002; Kyriakopoulos and Doulia
2006; Sarkar et al. 2007; Ohnoa et al. 2008; Kitous et al. 2009). The reported
adsorption capacity (170–422 mg/g) of AC depends on the source or the synthesis
process (Ayranci and Hoda 2005). Though it was found efficient for removal of
various pesticides such as 2, 4-D, endosulfan and uracil (Bromacil) but high regen-
eration cost, less availability and less-biocompatibility of commercialized AC has
limited its use (Hameed et al. 2009; Ignatowicz 2009; Mishra and Patel 2008) and
opened the gate for low cost and economical alternative adsorbents. Agricultural
waste such as sawdust and chemically and thermally treated melon peels, woods,
pine bark were found to be effective to immobilize methyl parathion, triazophos,
linuron and metalaxyl, heptachlor including several OCs pesticides (Rodriguez-Cruz
et al. 2008; Akhtar et al. 2009). Because of presence of acidic and hydroxyl groups
present in plants, they have high capacity to adsorb the pollutants through chemical
interactions (Ofomaja 2008). On further functionalization, the adsorption capacity of
these material are comparatively higher than raw materials and AC (El-Aziz et al.
2009). Polymeric resins such as amberlite, hydrogels etc. have been widely inves-
tigated because of their unique structures of polymeric chains and high adsorbing
power. (Chang et al. 2008; Aouada et al. 2009). Like agricultural waste, the residues
discharged from industries (sludge, fly ash, and carbon slurry) are also found to be
strong adsorbent for complete removal of toxic pesticides such atrazine, metolachlor,
metribuzin etc. (Sharma et al. 2008; Majumdar and Singh 2007). Low-cost in-or-
ganic adsorbents, for example, natural and organoclay complex adsorbents, have
been successfully used for the immobilization of industrial organic contaminants
(Sanchez-Martin et al. 2006), pesticides (Cruz-Guzman et al. 2005. Crystalline
zeolites (surface area: 903–1132 m2/g) are unique adsorbent materials with void
volumes of 18–50% (Ibrahim and Jbara 2009).
Degradation of Pesticides Using Nano-adsorbents
Degradation of all classes of pesticides using different nanomaterials are summa-

rized in Tables 6 (OCs pesticides), 7 (OPs pesticides) and 8 (Miscellaneous pesti-
cides) and discussed below in detail (Fig. 7).
Degradation of OC Pesticides
The vast research in development of innovative technologies for the rapid degrada-
tion of OCs into environmentally compatible compounds based on advanced process
is in progress. More recently, Rani et al. (2017a) has reviewed the nanomaterials
mediated degradation of OC pesticides. They observed that removal of those toxic
and persistent pesticides were mainly involving the use of TiO2 (photocatalysis) and
Fe0 (redox reaction). TiO2 is inexpensive, abundant, photostable, and non-toxic,
highly reactive and easily form highly active free radical species (OH•) on UV or
visible irradiation due to low band gap energy (Oncescu et al. 2010). In the presence
of nano-TiO2 coated film, only 32.0%, 44.0%, 0.2%, 9.0%, 31.0% and 0.4% of α-,
β-, γ-, δ-BHC, dicofol and cypermethrin, respectively, remained after 10 min and
complete photocatalytic degradation was observed within 2 h revealing the effi-
ciency of TiO2(Yu et al. 2007). Aldrin was quickly oxidized into dieldrin, chlordene
and 12-hydroxy-dieldrin in water system (Fig. 8) (Bandala et al. 2002). On doping
TiO2 with Nitrogen (1.6:1 molar ratio), its efficiency was increased more than double
(Fig. 6). By doping N (more electron rich) into the medium, the chemical statuse of
TiO2 changed into O–Ti–N, and hence, binding energy of Ti can be considerably
reduced (Chen and Burda 2004) (Fig. 9). The probable fact behind that is less-
electronegativeity of nitrogen than oxygen (Sathish et al. 2007). A proposed degra-
dation pathway of lindane with N-doped TiO2 is shown in Fig. 10 (Senthilnathan and
Philip 2010).
Another most investigated nanocatalyst is nZVI (Fig. 7) which reduced almost all
halogenated hydrocarbons to benign hydrocarbons by rapid and complete dechlori-
nation within 24 h (Wang et al. 2009; Shih et al. 2011). The advantage of nZVI lies in
its low cost, high efficiency, large surface area, non-toxicity and enormous flexibility
for in situ applications. Particle size of nZVI strongly influenced the degradation of
OCs. The degree of dechlorination of lindane was greater (>95%) for the nZVI
(60 nm) doses than that of commercial iron dosages (10 μm; 60% degradation).
Table 6 List of various OCs pesticides degraded using nanoparticles

Pesticide
(mgL1) Nanoparticles Brief summary Mechanism Reference
α-, β-, γ-, TiO2 coated Within 10 min; Photocatalytic Yu et al.
δ-BHC, dicofol films (2.24 mg/ 32%, 44%, 0.2%, degradation (UV) (2007)
and cm2) 9%, 31% and 0.4%,
cypermethrin respectively
(20 μg of each) remained
Dicofol TiO2 (0.25 mg/ Completely Photocatalytic Yu et al.
mL) degraded in 2 h, rate degradation (UV) (2008)
constant
(k) = 0.167/min
Aldrin (5) TiO2 (25 mg) Complete Photodegradation Bandala et al.
degradation into (2002)
dieldrin, chlordene
and 12-hydroxy-
dieldrin in water
Lindane Degussa P-25, Effectively Photodegradation Senthilnathan
(5 104 Anatase TiO2, degraded (100%) and Philip
mmol L1) N-doped TiO2 under visible light, (2010)
k = 0.099/min,
0.117 min1,
0.007 min1
Lindane(7.5) Zero-valent Quantitatively Reductive Elliott et al.
iron (Fe0) metabolize into degradation (2009)
(0.015 gL1) benzene and
chlorides within
24 h;
k = 3.62 102/h
Endosulfan Fe0 Removal of Adsorption, Pillai and
(1140 μgkg1) (1000 mgkg1 endosulfan from soil reductive Kottekottil
of soil) using Chittaratha (8% degradation (2016)
removal in 28 days),
Tulsi (20% in
28 days) and
lemongrass plant
DDT (10) Fe0 (1 gL1) Effective Reductive El-Temsah
degradation in water degradation et al. (2016)
(92%) than soil
(22.4%)
Endosulfan (1) Copper Completely Degradation Mitra and
annihilates in Varshney
solution (2013)
Lindane, DDT Fe based 100%, 81%, and Redox Shoiful et al.
and aldrin (10) compounds 79%, respectively degradation (2016)
(0.5 g, 1 g, and after 12 h reaction
2 g each) rate constants
0.1381, 0.0327,
0.0269
(continued)
Table 6 (continued)
Pesticide
Lindane (5) FeS stabilized 94% of degradation Oxidative Paknikar et al.
by in 8 h degradation (2005)
biopolymers
(culture
suspension
1 ml of 0.1 O.
D.600)
Aldrin, Endrin, Fe3O4 24.7 mg g1, Adsorption Jing et al.
Lindane supported on 33.5 mg g1, (2013)
polystyrene 10.2 mg g1
DDT (150 mL Bimetallic Effective Redox Tian et al.
of 100 μg Ni/Fe degradation in 4 h degradation (2009)
mL1) (0.05 gL1) with higher
efficiency in
alkaline or weakly
acidic medium,
k = 0.6073 s1
Lindane (1) Bimetallic Degraded Redox Joo and Zhao
Fe-Pd (0.5 g effectively under: degradation (2008)
L1) aerobic (65%;
Fenton-like process)
and anaerobic
(100%; reduction
process) conditions
Di and tri ZnO/γ- 55.2 and 57.0% Photocatalytic Abdullah
Chlorophenoxy Fe2O3(0.20 g degradation et al. (2013)
acetic acid(20) L1)
4-Chloro C/ZnO/CdS 98.0% in 120 min Photocatalytic Lavand and
phenol (10) (0.05 g in degradation Malghe
100 mL) (2015)
Lindane Ag- reduced 99.9% Degradation Gupta et al.
grapheme (2015)
oxide
Complete dihaloelimination (reductive degradation) of lindane into benzene and

chlorides using ZVI nanoparticles are shown in Fig. 9 (Elliott et al. 2009).
Few reports show that nZVI degradation capacity of contaminants degradation is
lower in soils than in aqueous solutions because of lower diffusion of OC from soil
particles to the surface of nZVI particles (Wang and Zhang 1997; Varanasi et al.
2007). For examples, degradation of DDT in water (92%) is higher in water than in a
historically (>45 years) contaminated soil (22.4% of 24 mg kg1 DDT) (El-Temsah
et al. 2016). Similarly, Slower degradation of endosulfan from soil was observed
during nano-phytotechnological remediation using nZVI and three plant species
Chittaratha (8% removal in 28 days), Tulsi(20% removal in 28 days) and Lemon-
grass (Cymbopogoncitratus) (Pillai and Kottekottil 2016).
Table 7 List of various OPs pesticides degraded using nanoparticles

Pesticide
Terbufos (5) TiO2 (50 mg) ~99% degradation Photocatalysis Wu et al.
within 90 min, rate (2009)
constant
k = 0.0854 min1
Monocrotophos, TiO2- zeolite (50 mg) 100% Photocatalysis Gomez
Dichlorv (20) et al.
(2015)
Acephate (10) TiO2 (4 gL1) Complete minerlization, Photocatalysis Han et al.
rate constant (0.6 mmol/ (2009)
(min L)
Phoxim (20) La-doped TiO2 (0.5 g Complete mineralization Photocatalysis Dai et al.
L1) after 4-h (2009)
Monocrotophos, ZnO/TiO2 (0.1 gm) 84.2% and 96%, Photocatalysis Kaur et al.
quinalphos respectively, (2013)
(20 each) k = 0.00567 min1 and
0.00199 min1
respectively
Malathion ZnO, TiO2, Au/ZnO, 30.0% degradation Photocatalysis Fouad and
(10 ppm) (104, 3 105, within 30 min Mohamed
105 M) (2012)
Malathion (12) TiO2 (anatase)/ WO3 Complete degradation Photocatalysis Ramos-
(2 wt.%) (125 or after 2 h Delgadoa
250 mg) et al.
(2013)
Malathion (10) Fe0 (0.1 g.kg1) Quantitative oxidation Oxidation Singhal
in soil within 8 min et al.
(2012)
Chlorpyrifos, Coating of Fe- With H2O2 (100 mg/L), Oxidation Affam et al.
Cypermethrin, granular-activated complete degradation in (2015)
carbon (5 gL1) 1 min
Chlorothalonil K = 0.017–0.024 min1
Chloropyrifos Au and Ag supported Complete degradation Adsorption Bootharaju
(10) on neutral alumina within 3 h using and
(100 mg at a loading supported Ag Pradeep
of 0.5 wt %) (2012)
Monocrotophos ZnO supported on 100% degradation in 4 h Photocatalysis Tomasevic
(16) zeolite (1 or 5 gL1) et al.
(2010)
Malathion (2) CuO –chitosan 99.9%, (k = 0.53 g mg- Adsorption Jaiswal
(0.02 g) 1 min-1) et al.
(2012)
Chlorpyrifos (5) CoFe2O4@TiO2 89.9%in 60 min Photocatalysis Gupta et al.
-reduced grapheme (2015)
(0.4 g L1)
Dichlorvos CuO-MMT 83.2% Adsorption Sahithya
(20–100) (0.5–3.0 g L1) et al.
(2015)
(continued)
Table 7 (continued)
Pesticide
Dichlorvos CuO-MMT 93.4%, 87.8% and Adsorption Sahithya
(20–100) supported on 63.3% removal, et al.
chitosan, gum ghatti respectively (2015)
and poly lactic acid
(0.5–3.0 g L1)
Parathion methyl Titania-iron mixed Highest degradation SN2 Henych
(PM) (100 μL of oxides(50 mg in (<70%) with Ti:Fe ratio et al.
10,000 mg /L) 400 μL) 0.25:1and 1:0.25 (2015)
PM(100 μL of Titania-ceria mixed Degradation ability: SN2 Henych
10,000 mg /L) oxides(50 mg in Nano-ceria> nano- et al.
400 μL) titania; highest (2016)
degradation at Ti:Ce 2:8
and 1:1 molar ratio
PM (200 μL of MnO2 (IV) (50 mg in 90% within 2 h in SN2 Stastny
5000 mg/L) 300 μL) non-polar organic et al.
solvent (2015)
PM, CeO2 (1 g CeO2) 90% of degradation in SN2 Janos et al.
chlorpyrifos, 1 min, cleavage of the P- (2014)
dichlofenthion, O-aryl bond
fenchlorphos,
prothiofos
(20 mg)
Although nZVI have many advantages but its efficiency decrease with time
because of formation of oxide layers which block its surface-active sites. Therefore,
in order to enhance the speed and efficiency of remediation modified iron nano-
particles have been synthesized. Magnetite (Fe3O4) containing Fe2+ triggers the
formation of free radical in photocatalytic processes, thereby initiating the degrada-
tion reaction (Fig. 10) (Rodriguez et al. 2011). Thus, the combination of ZVI and
magnetite forms a highly reactive material which successfully and quickely
degraded organic compound (Moura et al. 2005, 2006).
ZVI and magnetite (Fe3O4) reducing the time from 24 h (as reported by Elliott
et al. 2009 and El-Temsah et al. 2016) to 12 h for following OC pesticides in water:
γ-HCH (100%) > DDT (81%) > aldrin (79%) (Shoiful et al. 2016). Iron sulfide
nanoparticles stabilized by biopolymers found to be more effective than nZVI and
combination of ZVI with magnetite (Fe3O4) degraded 94% of lindane within 8 h
(Paknikar et al. 2005). Lindane was degraded effectively under aerobic (65%; Fenton-
like process) and anaerobic (100%; reduction process) conditions with bimetallic
Fe-Pd (Joo and Zhao 2008). Bimetalllic Pd/Fe a nanocomposite of iron with Pd could
able to degrade almost all OCs pesticides only at dose of 6.25 g/l within 8 h. Tian et al.
(2009) tested the efficiency of bimetallic Ni/Fe nanoparticles in the degradation of
DDT in aqueous solution. pH studies revealed that higher degradation of DDT was
observed at weakly acidic or alkaline conditions. A tentative degradation mechanism
of DDT in alkaline medium is depicted in Fig. 11.
Table 8 List of various miscellaneous pesticides (including carbamate and pyrethroid) degraded
using nanoparticles
Bulk/
Pesticide(mgL1) nanoparticles Brief summary Mechanism Reference
Methomyl Fe-zeolite 100% degradation in 4 h Photocatalysis Tomasevic
(16) (carbamate) (1or 5 gL1) et al.
(2010)
Pyridazinone Pesticides
Chloridazon (10) Au/TiO2 50% in 30 min Photocatalysis Fouad and
(104, Mohamed
3 105, (2012)
105 M)
Chloridazon(20) Fe3O4 and >90% degradation Photocatalysis Fouad and
coreshell Mohamed
Fe3O4@Au (2011)
(104 M)
Chloridazon TiO2 (1 g Acidic condition: Photocatalysis Khan et al.
(125 mL; L1) Chloridazon> (2012)
0.18 mM) and metribuzin
Metribuzin Alkaline condition:
(125 mL of Metribuzin >
0.30 mM) Chloridazon
Permethrin ZnO- 99% Adsorption Dehaghi
(25 ml, 0.1 mg chitosan et al.
L1) (Pyrethroid (0.5 g) (2014)
pesticide)
Neonicotinoids Pesticides
Thiamethoxam TiO2 (1 g TiO2 P25 is more Photocatalysis Mir et al.
(3.4 mM) L1) efficient photocatalyst (2013)
than UV100 and PC500
Acetamiprid TiO2 More efficiently Photocatalysis Khan et al.
degraded in alkaline pH (2010)
and all electron
acceptors enhanced the
degradation rate
Imidacloprid, Immobilised Mineralized within 2 h Photocatalysis Zabar et al.
Thiamethoxam, TiO2 with k = 0.035, 0.019 (UV) (2012)
Clothianidin and 0.021 min1,
respectively
Imidacloprid, 5 wt% TiO2 At neutral pH, Photocatalysis Sharma
Isoproctum, supported on degradation within (UV) et al.
Phosphamidon porous 90, 240, and 120 min, (2009)
(1.14 104 M nanosilica respectively
each) (3 g L1)
Thiamethoxam, Zero-valent Degradation >90% after Ultrasonication Lopes et al.
(20 mL; 50 mg metals (Fe, a reaction time of (2008)
L1) Sn, Zn) 30 min via initial NO2 –
Imidacloprid (0.06 mol > NH2 reduction
(20 mL; 35 mg L1)
L1)
(continued)
Table 8 (continued)
Bulk/
Pesticide(mgL1) nanoparticles Brief summary Mechanism Reference
Thiamethoxam, Fe /Fe3O4 > 90% in 30 min, Redox De Urzedo
(20 mL; 50 mg (0.06 mol highly efficient in acidic degradation et al.
L1) L1) conditions (2009)
Imidacloprid With/or
(20 mL; 35 mg H2O2
L1)
Atrazine (2 g) Ag-chitosan 98% degradation in Adsorption Saifuddin
(1 L of 1 mg 65 min et al.
L1) (2011)
Atrazine Carbon >90 degradation Adsorption Yan et al.
nanotubes (2008)
Fig. 7 Mechanism for the working of zero-valent iron (ZVI) under different conditions
Nanocomposite of Fe3O4 supported on polystyrene degraded aldrin, endrin and

lindane via adsorption mechanism (Jing et al. 2013) while combination of C/ZnO/
CdS photocatalytically degraded 98.0% of 4-Chloro phenol (Lavand and Malghe
2015). Scattered information is also available in literature on the use of Cu and
supported on reduced graphene for the degradation of endosulfan (Mitra and
Varshney 2013) and lindane (Gupta et al. 2015), respectively.
Degradation of OP Pesticides
After OCs, the pesticides having great environmental concern are OPs because of
their abundant use, toxicity and residue detected in environment. The complete
degradation of organic pollutants is not possible by conventional approaches
such as digestion (activated sludge, anaerobic etc.) and physicochemical
treatment (Galindo et al. 2001; Kuo and Ho 2001; Tang and An 1995). Sud and
Kaur (2012) reviewed the importance of heterogeneous photocatalytic degradation
of several OP pesticides. These photocatalysts do not operate at room temp-
erature without aid of irradiation system. Therefore, in addition to photocatalysis,
Fig. 8 Rapid reactive adsorption of parathion methyl on MnO2 (Stastny et al. 2015)
rapid reactive adsorption were highly proposed for remediation of OPs in

wastewater.
Like OCs, TiO2 as such, modified, doped and composites were investigated along
with ZVI and other noble metals for degradation of OPs such as methamidophos
malathion Parathion etc. by heterogeneous photocatalysis (Doong and Chang 1997;
Xu et al. 2002; Moctezumaa et al. 2007; Zhang et al. 2006; Kralj et al. 2007). Under
UV exposure and aqueous medium, TiO2 could complete mineralized (99% photo-
degradation) acephate (Han et al. 2009) while terbufos could converted into eight
intermediates within 90 min (Fig. 12) (Wu et al. 2009).
These findings have showed that OP’s degrade rapidly and non-selectively
with TiO2. Also, the oxidation strength of the UV/TiO2 photocatalysis is enhanced
by the addition of H2O2 than UV/TiO2 photocatalysis (Fig. 6) in degradation
Fig. 9 Proposed degradation pathway of lindane using N-doped TiO2 (Senthilnathan and Philip
2010) and zero-valent iron (Elliott et al. 2009)
Fig. 10 Role of magnetite in

oxidative degradation of
pesticides (Rodriguez et al.
2011)
Fig. 11 Tentative degradation pathway of DDT using Ni/Fe bimetallic nanoparticles (Tian et al.
2009)
of pesticides chlorpyrifos, cypermethrin and chlorothalonil in aqueous solution

(Fig. 13).
In case of mixed photocatalyst (ZnO/TiO2), the maximum degradation of mono-
crotophos and quinalphos has been observed when ZnO and TiO2 were in the ratio of
7:3 and 8:2 respectively (Kaur et al. 2013). The degradation efficiency with synthe-
sized heterostructured nanophotocatalyst was found to be comparable with TiO2.
Solar photocatalytic activity of WO3/TiO2 was evaluated using malathion as a model
contaminant (Fig. 14). Best results were obtained using 2% WO3/TiO2(complete
degradation) after 2 h, whereas, 5% WO3/TiO2 and bare TiO2 achieved 28% and
47% mineralization, respectively (Ramos-Delgadoa et al. 2013). Degradation of
malathion increased by 172% when modified TiO2 (Au-Pd-TiO2 nanotube film)
was used (Fig. 13) (Yu et al. 2010).
Fig. 12 Proposed photocatalytic degradation pathway of terbufos (Wu et al. 2009)
The feasibility of nanocomposite such as TiO2SiO2 beads, IO3 doped TiO2, La
doped ZnO, TiO2 supported on Zeolite and La-doped TiO2 were employed for
eradication of monocrotophos with dichlorvos (Shifu and Gengyu 2005; Gomez
et al. 2015) and phoxim (Dai et al. 2009). Doping of TiO2 latice with metal ions
might cause an increase in the formation of Ti3+ ion and more surface defects (which
depend on the doping identity and concentration) and facilitate efficient adsorption
of oxygen on titania surface. Metal ion work as charge carrier traps and effectively
enhances the charge separation of electrons and holes resulting in increase in the
quantum yield of surface photo reaction. Since the redox energy state of several
metal ions lie within the band gap of TiO2, addition metal ions into TiO2 introduces
new energy levels between CB and VB edge and absorption was due to the charge
Fig. 13 Photodegradation of malathion in presence of TiO2/WO3 (Ramos-Delgadoa et al. 2013)

and Au-Pd-TiO2 nanofilm (Yu et al. 2010)
transfer transition between the d electrons of dopant and CB or VB of TiO2

(Ramacharyulu et al. 2014) (Fig. 14).
Addition of iron compounds (Fe0, Fe2+) could able to enhance the degradation
efficiency of OPs similar to OCs via electrochemical reaction (Joo et al. 2004; Hung
and Hoffmann 1998; Zhang 2003). In contaminated soil (1–10 μgg–1), quantitative
oxidation of malathion into metabolits O-dimethyl phosphorodithioic (non-toxic to
human or any other living beings) was achieved with n-ZVI (33–78 nm) within
8 min in ambient environment (Singhal et al. 2012). Degradation kinetics was
surface area dependent clearly pointed out that higher specific surface area of iron
particles is desired for faster degradation. For example, chlorpyrifos, cypermethrin
and chlorothalonil was completely and rapidly degraded in 1 min by coating of
Fe-granular AC and H2O2(FeGAC/H2O2), via oxidative mechanism (Fig. 15)
(Affam et al. 2016).
Here, presence of AC increase the adsorbing properties of iron because of its high
surface area. AC as an electron donor reduces the ferric ion to ferrous ion and
Fig. 14 Photodegradation of
chlorpyrifos, cypermethrin
and chlorothalonil with
Fe/GAC (granular activated
carbon) (Bach and Semiat
2011; Affam et al. 2015)
Agn+
Agn+
Agn+ Agn+
Agn+
Fig. 15 Degradation of chlorpyrifos (CP) on Ag nanoparticles (Bootharaju and Pradeep 2012)
combination of ferrous/ferric ions and H2O2 are used to generate excess of OH•
(Bach and Semiat 2011).
Another metals employed for the degradation of various OPs are Ag and Au
supported or modified with other materials. Under solar as well as UV, pesticides
containing phenol were effectively removed by Ag@TiO2 at pH~ 3 due to the
interactions between positively charged TiO2 surface and negatively charged
phenols and intermediates (Shet and Shetty 2015). Chlorpyrifos (CP) was degraded
using Penicilliumpinophilum derived Ag nanoparticles with consistently highest
degradation observed in mild acidic condition (pH 6) irrespective of incubation
time (Deka and Sinha 2015). Noble metals have also efficiency to degrade OPs at
room temperature. For example, CP is shown to decompose to 3,5,6-trichloro-2-
pyridinol(TCP) and diethyl thiophosphate over Ag and Au NPs supported on neutral
alumina (Fig. 15) Bootharaju and Pradeep (2012). Complete degradation of CP
occurred within 3 h through the formation of AgNPS surface complex where
PO bond cleaves to yield a stable aromatic species, TCP.
In addition to these catalysts, some other catalysts were also proved to be
effective in the degradation of hazaradous OPs like ZnO and PbO2. ZnO nano-
particles were proved to be a time saving photocatalyst for the degradation of
Chlorpyrifos with degradation rate increased several times when photocatalytic
reactor was combined with membrane filteration (Khan et al. 2015). Using
Bi-doped PbO2 electrodes several pollutants from wastewater were removed suc-
cessfully, particularly Tebuconazole-TBC into less toxic products than TBC
(de Figueredo-Sobrinho et al. 2015). Overall, due to high adsorbing properties and
semiconducting nature, nanophotocatalysts (TiO2, Ag, Au, ZnO, PbO2) become
efficient adsorbent and generate free radical upon irradiation. This free radical is
responsible for the degradation of hazardous OPs pesticides in a short duration of
time. Similarly, the chitosan based nano-biocomposites were proved to show the
higher removal of organophosphate pesticides (Jaiswal et al. 2012; Dehaghi et al.
2014). Higher removal of dichlorvos by CuO-montmorillonite-chitosan and
CuO-montmorillonite gumghatti nano-biocomposites suggested that biopolymers
can play major role in the adsorption of pesticide (Sahithya et al. 2015). Nano-
composites ZnO – Zeolite and CuO-Chitosan completely degraded Monocrotophos
(Tomasevic et al. 2010) and Malathion (Jaiswal et al. 2012) via Photocatalytic and
Adsorption mechanism, respectively.
Another most extensively field used for fast destruction of toxic pesticides into
less toxic residuals is use of potential reactive sorbents such as nanostructured metal
oxides of Mg, Ca, Ti, Mn, Fe, Zn, Al, and Ce (Houskova et al. 2007; Chen et al.
2010; Štengl et al. 2016). MgO, Al2O3 and CaO titania nanotubes, manganese oxide
nanotubes remove the agent rapidly owing to their high surface area, strong
adsorbability and potential reactivity (Talmage et al. 2007). MnO2 and various
oxides were effectively used in 90% decomposition of parathion methyl within 2 h
by cleavage of the P–O-aryl bond in the pesticide (Fig. 8). These promising materials
are prepared via homogeneous hydrolysis and exhibit a capability to capture and
degrade toxic OP compounds via nucleophilic substitution SN2on their surfaces
even at ambient temperature i.e., rapid reactive adsorption (Khaleel et al. 1999;
Mitchell et al. 2004). They are first time developed by Klabunde, and his research
group and used for the destruction of chemical warfare agents and analogues OPs
(Klabunde et al. 1996; Khaleel et al. 1999; Lucas and Klabunde 1999). It was found
that exhibit a comparatively higher degradation activity. Mixed or doped oxides with
unusual structural features and properties are promising materials for preparing
reactive sorbents than pure oxides. Ti/Ce mixed oxides or composites are used in
heterogeneous catalysis (Gao et al. 2010) due to unique redox properties

(Rynkowski et al. 2000). Henych et al. (2016) studied there active adsorption of
toxic parathion methyl and DMMP on nanostructured Ti/Ce oxides and their com-
posites. Nano-ceria exhibited substantially higher degradation ability compared to
nano-titania. The highest degradation efficiency was achieved with the composites
with Ti:Ce 2:8 and 1:1 molar ratio. Interestingly, the degradation efficiency of the
TiO2/CeO2 composites is moderately higher than that of pure CeO2.The strong
interaction of Ti with Ce led to an increase of Ce3+ and formation of Ti4+ states
and changed surface area and porosity which may cause improved degradation
efficacy for both DMMP and parathion methyl.
In addition to metal oxides, the use of metal-organic frameworks (MOFs)
and organocatalysts as reactive adsorbent are also in progress. MOFs are crystal-
line metallo-organic compounds with a well-defined geometric structure
consisting of metal ions or clusters coordinated to organic ligands. Some of the
Zr-based MOFs and their rare earths analogues were tested for the degradation of
organophosphate pesticides. The study of Barba-Bon (2015), who examined a
series of different amines, aminoalcohols and glycols as potential organocatalysts
for DCNP (diethylcyanophosphate) degradation, may serve as an example. It was
found that some of the functionalized sorbents are capable to destroy parathion
methyl and convert it to 4-nitrophenol in a similar way as the metal oxide-based
reactive sorbents. On contrary to the metal oxide-based reactive sorbents,
the degradation proceeds in aqueous solutions, although the rate of degradation
is lower.
Degradation of SU Pesticides
In spite of a less persistence in soil and water (Zhou et al. 2009), their chronic
exposure and long-term toxicity effects were observed via food chain. Chemical
hydrolysis and microbial degradation of SU in soil is influenced by pH, moisture
content and microbiological activity (Saha and Kulshrestha 2008; Si et al. 2005).
The dissipation of two SU herbicides, chlorsulfuron(t1/2 = 6.8–28.4 days)and
imazosulfuron(t1/2 = 6.4–14.6 days) was faster in acidic medium(Wang et al.
2010). Saha and Kulshrestha (2008) carried out pH dependent hydrolytic degrada-
tion of sulfosulfuron with faster hydrolysis rate in acidic condition (t1/2 = 9.24 days;
pH 4.0) than alkaline (t1/2 = 14.14 days; pH 9.2). Under abiotic conditions, the major
degradation mechanism of the compound was the breaking of the sulfonylurea
bridge yielding corresponding sulfonamide and aminopyrimidine (Saha and
Kulshrestha 2008).
The ultraviolet (UV) radiation in the sunlight is one of the most powerful forces
for pesticide degradation. Photolysis of imazosulfuron was reported inaqueous
solution in UV light under aerobic (chemical cleavage) and anaerobic (microbial
degradation)conditions (Wang et al. 2010).
Diflubenzuron is quickly degraded in the environment mainly by hydrolysis
and photodegradation producing major metabolites: 2, 6-diflurobenzamide,
4-chlorophenylurea, 4-chloroacetanilide, 4-chloroaniline and N-methyl-4-

chloroaniline, which are classified as mutagens (Rodriguez et al. 1999).
Senthilnanthan et al. (2010) carried out photocatalytic degradation of metsulfuron-
methyl in aqueous phase under visible light with using TiO2 (40%) and Ru doped
TiO2 (80%).
Use of nanoparticles for the degradation of SU pesticides is still awaited.
No doubt these pesticides have comparatively lower half-lives than the OCs
or OPs, but once the threshold limit is exceeded, these can cause severe damage
to the environment due to their toxicity. Keeping in view the future aspects,
their use should be limited or banned. Presently, to eliminate the persisting SU
from the environment, various nanomaterials can be employed with high
degrading efficiencies. This opens a research gap for the researchers working in
this field.
Degradation of Carbamate Pesticides
Because of the variety of different groups present in carbamateinsecticides, the

metabolism of these compounds is often complex. Carbaryl, for example, is a
relatively simple compound, yet it is metabolized to at least 15 different com-
pounds in mammals through a variety of oxidative and hydrolytic reactions
(Leeling and Caisida 1966). Scattered informations on biodegradation on carba-
mate are moving slightly to use of nanophotocatalyst. A study showed that the
urine from carbaryl-treated rabbits contained at least four or five other water-
soluble metabolites (glucuronides or sulfates). Tien et al. (2013) used natural river
biofilms to degrade the carbamate pesticides methomyl, carbaryl and carbofuran.
Certain metabolites of carbamates such as 1-naphthol are found in the urine as
1-naphthyl glucuronide and/or 1-naphthyl sulfate. Sullivan et al. (1972) identified
one of these metabolites, 5,6-dihydroxy carbarylglucuronide, in the urine of rats.
Doddamani and Ninnekar (2001) isolated Micrococcus species from garden soil
and used for the degradation of carabaryl (Fig. 16) into 1-naphthol and methyl-
amine, further metabolized by oxygen uptake. Degradation of aldicarb under UV
radiation was carried out by Dixit et al. (2009) using TiO2/polyacrylonitrile
nanofiber into lesser toxic third oxidation oxime product (Fig. 17). Photo catalytic
oxidation of Methomyl by Fe supported on Zeolite resulted in complete removal
(Tomasevic et al. 2010).
It is evident from the above the information that the literature available on the
degradation of carbamates using nanoparticles is very scarce. Since these are a new
class of pesticides, therefore, not much attention has been paid to their degradation
using advanced technologies. After one or two decades, these pesticides may cross
their threshold limit and ultimately will affect the environment. To avoid this
situation, prior efforts must be made. In this context, use of nanotechnology is highly
recommended.
Fig. 16 Degradation pathway of carabaryl by Micrococcus species (Doddamani and Ninnekar)
Fig. 17 Proposed pathway showing third oxidation of aldicarb using TiO2 catalyst (Dixit et al.
2009)
Degradation of Miscellaneous Pesticides
Heterogeneous photocatalysis using TiO2 as photocatalyst appears as the most

emerging destructive technology for all pesticides including well known OCs and
OPs. Complete photodegradation of imidacloprid (90 min), isoproctum (240 min),
phosphamidon (120 min) was achieved using 5 wt% TiO2 supported on porous
nanosilica (under neutral pH conditions) (Mangalampalli et al. 2009). Minerali-
zation rate was enhanced in the presence of TiO2 containing H2O2 due to the
efficient generation of hydroxyl radicals. Degussa P25, was found to be more

efficient catalyst for the degradation of both herbicides chloridazon and metribuzin
as compared with two other commercially available TiO2 powders like Hombikat
UV100 and PC500 (Khan et al. 2012). Chloridazon was found to degrade more
efficiently under acidic condition, whereas metribuzin degraded faster under
alkaline medium. Similar observation were found for photocatalytic degradation
of Thiamethoxam. Photocatalysis of Thiamethoxam follows pseudo-first-order
kinetics. An increase of the degradation percentage was observed for removal of
chloridazone on using Au/ZnO and Au/TiO2 and also a reduction of the radiation
rate time, which is due to the presence of the gold which prevents the electron hole
recombination and accelerates the photodegradation (Fouad and Mohamed 2012).
In addition to TiO2 zero-valent metals in the presence of ultrasonic irradiations
(Lopes et al. 2008) and Fe /Fe3O4 composite were found efficient in promoting the
degradation of thiamethoxam and imidacloprid in acidic aqueous solution. Dual
behavior of Fe /Fe3O4 composite as a reducing or an oxidizing agent was found
depending on absence or presence of H2O2, respectively. Fe3O4@Au has turned
out to have high efficiency in photodegradation of chloridazon under UV and
sunlight in comparison to the Fe3O4 due to the presence of the gold which has
the plasmonic phenomena having a great influence in accelerating the oxidation
of the pesticides (Fouad and Mohamed 2011). Silver supported on chitosan
adsorbed 94.0% of Atrazine (Saifuddin et al. 2011) and demonstrated the
high removal capacity of synthesised Ag/chitosan nano-biocomposite. During
the removal of pesticide atrazine on CNTs, Yan et al. (2008) inferred that the
surface area might not be the only factor that determines the adsorption capacity;
other factors such as surface chemistry would also influence the adsorption
processes. Carbon nanotubes (CNTs) are most efficient adsorbents because
of their unique chemical structure and intriguing physical properties (high surface
area, high reactivity) that helps in formation of strong interaction between organic
chemicals and CNTs (Long and Yang 2001; Fugetsu et al. 2004; Mauter and
Elimelech 2008).
Utilization of Green Synthesized Nanomaterials in Remediation

of Environment
Nanomaterials generated via green route are cheap. Currently, a lot of researchers
worldwide are working on synthesis of nanoparticles using by employing sunlight,
or plant-based surfactants or microorganisms and water or combination of those.
Application of these nanoparticles in the degradation of harmful pesticides will help
in reconstructing the polluted environment. There are some examples highlighting
the use of green synthesized nanomaterials in removal of various organic pollutants
and provide the feasibility in treatment of pesticides in wastewater.
Recently, sunlight assisted green synthesis of various transition metal oxide
(ZnO, CuO, Co3O4, NiO and Cr2O3) nanoparticles and their catalytic application
in removal of organic colorants were studied (Shanker et al. 2016b). Interestingly, in
a short period of 180 min, 88% of the dyes was more or less completely degraded
using Cr2O3, ZnO followed by >87% (CuO) >86% (NiO) >80% (Co3O4),
depending on the sizes of respective nanoparticles. Employing a green route Jassal
et al. (2016b) synthesized different potassium metal hexacyanoferrate (KMHCF)
nanoparticles using Aegle marmelos as a natural surfactant and utilized them for the
degradation of various dyes. 94.72% of the dye was degraded using KCuHCF
followed by 91.35% using KNiHCF and 89.28% using KCoHCF nanoparticles
(Jassal et al. 2016b). Using Morinda tinctoria leaf extract silver nanoparticles were
synthesized and effectively degraded 95% of dye in 72 h under sunlight irradiation
(Vanaja et al. 2014). In addition to this, Polygonum Hydropiper was also used as a
biogenic source for synthesizing silver nanoparticles with high catalytic efficiency in
degrading MB completely within 13 min (Bonnia et al. 2016). Yeast (Saccharomy-
ces cerevisiae) extract was also utilized for synthesizing silver nanoparticles which
were effectively applied for degrading ~90% of MB within 6 h (Roy et al. 2015). A
high degradation of 98% for Orange II was reported using green synthesized
bimetallic Fe/Pd nanoparticles, whereas, only 16% of the dye was degraded using
Fe nanoparticles (Luo et al. 2016). Green synthesized copper oxide nanoparticles
and ZnO/Graphene Oxide (GO) nanocomposite were also used for decolorization of
the dye (Sankar et al. 2014; Lellala et al. 2016)
Conclusions and Future Scope
This review covered the encouraging performances of a variety of nanomaterials and

nanocomposites as adsorbent, heterogeneous redox and photo-catalyst or reactive
sorbents for the effective degradation of pesticides (Rani et al. 2017b; Rani and
Shanker 2017b; Jassal et al. 2015a, b, c; Jassal et al. 2016a). Nanomaterials not only
adsorb the pesticides, but also degrade them into non-toxic by-products. Being
inexpensive, commercially available, non-toxic in nature, and of high efficiency,
TiO2 and nZVI have emerged as a promising wastewater treatment technology in the
last few years (Shanker et al. 2016a, b, 2017a, b, c; Rani et al. 2017b). Majority of
the nanoadsorbents are able to degrade more than 80% of the pesticide and various
even achieved complete degradation in a short span of time. Further, the band gap of
TiO2 can be altered via the insertion of other metal oxides or electron rich elements.
Addition of H2O2 enhanced the oxidative efficiency of nanomaterials because of
production of more •OH radical. Nanocrystalline reactive adsorbents such as metals
(Mg, Ca, Ti, Mn, Fe, Zn, Al, Ce) by itself or in mixture(e.g., Ti/Ce) and their oxides
are found to have potential against OPs at ambient temperature. Further, nano-
composites such as ZnO/clay, Fe/zeolite and TiO2/zeolite and nanobiocomposites
like TiO2/chitosan were being used due to their enhanced activity and biocompati-
bility. OCs and OPs are frequently degraded by nanomaterials but carbamates and
SU (future contaminants) have not been explored extensively yet. Nanomaterials
mediated studies on different traditional or upcoming pesticides are imperative in
order to ban or restrict them. Finally review ends with suggested future scope of
using green synthesized nanomaterials that would be cheaper and effective catalysts.
For sustainable developments, biopolymers-based nano-biocomposites should be
developed.
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insecticides in peach juice drink by floated organic drop microextraction-high performance
liquid chromatography. Anal Lett 42:1805–1819
Treatment of Domestic Gray Water by
Multicomponent Filters 54
R. M. S. Radin Mohamed, Adel Al-Gheethi,
Muhammad Shabery Sainudin, and M. K. Amir Hashim
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1342
Grey water Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1344
Grey water Treatment by Filtration Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1345
Ceramic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1346
Size and Surface of Media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1348
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1348
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1349
Abstract
This review described, summarized, evaluated, and clarified the related theories
and previous research relevant to bathroom gray water quality and its design
treatment system to reduce the contamination of gray water. It provides a theo-
retical base for research and helps in determining the nature of the research. In
addition, this chapter may also serve as a handy guide on the use of ceramic
filtration for bathroom gray water.
Keywords
Bathroom gray water · Design treatment system · Contamination
R. M. S. Radin Mohamed (*) · A. Al-Gheethi (*) · M. K. Amir Hashim

e-mail: maya@uthm.edu.my; adel@uthm.edu.my
M. S. Sainudin
Micro-Pollution Research Centre (MPRC), Department of Water and Environmental Engineering,
Faculty of Civil and Environmental Engineering, Universiti Tun Hussein Onn Malaysia, Parit Raja,
Johor, Malaysia

https://doi.org/10.1007/978-3-319-73645-7_34
1342 R. M. S. Radin Mohamed et al.
Introduction
The water pollution is a major global problem and requires ongoing evaluation and
revision of water resource policy at all the levels. The increasing of water pollution
due to the direct discharge of wastewater into the natural water systems is associated
with the growth rate of the population as well as the rapid construction development
(Mohamed et al. 2014, 2016). Therefore, it can be stated that most of the environ-
mental issues are arising from human, commercial, domestic, or industrial activities.
Grey water in the rural regions is one of the major sources of pollution because it
contains different chemical substances such as xenobiotic and detergents as well as
nutrients which are directly discharged into rivers without any treatment due to the
absence of central wastewater treatment plants (Figs. 1 and 2). These wastes are also
defined as the wastewater that resulted from the urban activities which include baths,
showers, handbasins, washing machines, dishwashers, and kitchen sinks, but not the
backwater from the toilets (Jefferson et al. 1999; Al-Gheethi et al. 2016). According
to Friedler and Galil (2003), around 60–70% of gray water are transformed from the
urban water demand of industrialized countries. However, the real quantities of the
gray water are depending on the lifestyle and household activities which are differing
from one country to another (Al-Mashaqbeh 2012).
Bathroom gray water has low contaminations in comparison with the blackwater
especially in terms of organic contents (Mohamed 2011). In some definition, these
waste are called the light gray water (Friedler and Hadari 2006); it represents 30% of
the total wastewater generated from each house (Lesikar 2005). However, it still
contains viruses and pathogenic bacteria from cleaning activities in the bathroom
Fig. 1 Flow of bathroom gray water to the drains (Photo was taken on 12 October 2016)
54 Treatment of Domestic Gray Water by Multicomponent Filters 1343
Fig. 2 Main drainage conditions (Photo was taken on 12 October 2016)
such as body washing, laundry, and nappy washes. Mohamed et al. (2013) stated that
the bathroom gray water has nutrients as phosphorus and nitrogen which is coming
from the detergents used in laundries activity. The discharge of untreated bathroom
gray water might cause unpleasant odors and increase the insect attraction; the
presence of nutrients in the gray water creates ideal surroundings for bacteria growth
and thus attracts for insect pests to breed (Mohamed et al. 2014).
Filtration method is one of the most efficient technologies used for treating of gray
water. The filtration media from natural sources such as sand, clamshell, charcoal, and
gravel have been investigated to determine their efficiency in removing pollutants
from the wastewater. These materials are more applicable because they are easy to be
handling, sustainable with low cost (Siracusa and La Rosa 2006). The combination
between different natural materials in the design a filtration system for the treatment of
gray water has been reported in literature (Mohamed et al. 2016). The most common
natural materials used as filter are fine particles such as ceramic (fired clay) which
exhibited high efficiency in removing lead (Pb) by 100%, sulfate SO2− 4 by 76%, iron
(Fe) by 47%, and fluoride by 75% from the wastewater (Erhuanga et al. 2014). The
present chapter has focused on highlighting a sustainable treatment process of bath-
room gray water in the village house by using filtration media.
Ayer Hitam is one of the towns in Johor and is well known for ceramic production
industries. The town is rich in kaolinite which is the main raw material in the ceramic
industries. All kinds of ceramics, including garden decorative items, kitchenware,
home furnishings, and souvenirs, are available in this town. Figure 3 shows the
ceramic waste disposed at the side of the store. The improper dumping of these
wastes produces a significant visual impact and environmental degradation (Juan
et al. 2010). Therefore, the importance of ceramic waste recycling as filtration
system for gray water lies in introducing a new filtration media. Although the
bathroom gray water water are less polluted, it also needs to be treated due to the
Fig. 3 Ceramic wastes from

“AS Highway Enterprise
Pusat Perkahwinan
Kraftangan Bunga”
presence of several various chemical agents such as detergents, solvents, organic

acids, and bleaching agents which might be the reason for serious health problems.
These pollutants are qualitative pollutants and might be more serious than the
quantity pollutants such as nutrients and pathogens.
Grey water Characteristics
Grey water is wastewater generated from the households or building activities

without fecal contamination. It is also defined as the urban wastewater from bath-
rooms, handwashing basins, laundry, and kitchen excluding toilet waste (Jefferson
et al. 1999; Ottoson and Stenström 2003). Grey water are derived from the residen-
tial area, school, and office building; it contains traces of dirt, food, grease, oil, and
certain household cleaning products depending on the source. The quantity and
quality of gray water are quite different from one house to another as well as from
one time to another due to the type of personal care that has been used, shampoo
brand, and inclusion of urine and diaper washing in the bath (Mohamed et al. 2014).
Grey water is divided into three categories including laundry, bathroom, and kitchen
wastewater. In the residential, bathroom gray water represent 60% of the total gray
water; 40% are dishwasher, sink, and laundry gray water (Jamrah and Ayyash 2008).
The characteristic of gray water is highly different (Table 1). Among these wastes the
laundry gray water contains high concentrations of the pollutants due to presence of
powdered detergents which has high salt concentrations and phosphorus.
The characteristic of bathroom gray water produce in household activities
depends on the number of occupants, age, health status, lifestyle, and water usage
patterns (NSW Government 2008). As a result, the bathroom gray water may vary
greatly in physical, chemical, and biological characteristics. Moreover, the quality of
the bathroom gray water is characterized by the water quality test.
According to the previous studies presented in Table 1, it can be noted that the
physical, chemical, and microbiological characteristics of bathroom gray water
Table 1 Characteristic of bathroom grey water from previous studies

Ghaitidak and Eze et al.
Parameters Units Mohamed et al. (2014) Yadav (2013) (2015)
pH – 6.1 0.06–6.4 0.21 7.1–7.6 6.30 0.42
TSS mg/L 78 4.55–163 7.12 58–78 305.0 6.0
Turbidity NTU NR 59.8 41.0 1.0
BOD mg/L 40 0.25–105 0.42 129–173 9.7 0.10
COD mg/L 445 2.52–621 4.02 230–367 15.0 0.8
Ca mg/L 6 0.63–20 0.45 NR 40.10 2.0
Na mg/L 72 0.78–85 1.03 112 57.2 2.8
E. coli Cell/mL NR 82.7 NR
TN mg/L 10 2.90–38 0.56 6.6 NR
TP mg/L 3 0.87–20 1.76 NR NR
TSS total suspended solids, BOD biological oxygen demand, COD chemical oxygen demand,
TN total nitrogen, TP total phosphorus, NR non-reported
exhibited high differences. The total suspended solids (TSS) ranged from 58 to
305 mg/L, while biological oxygen demand (BOD) and chemical oxygen demand
(COD) were between 9.7 and 173 mg/L as well as between 15 and 621 mg/L,
respectively. The total nitrogen (TN) ranged from 6.6 to 38 mg/L, and total phos-
phorus (TP) ranged from 3 to 20 mg/L. However, these wastes have low load of
E. coli (82.7 cell/mL).
The bathroom gray water contains various elements generated from the utilization
of cleaning substances such as detergents. The detergents are known as the primary
source of phosphates in the gray water but not yet had been prohibited as
phosphorus-containing detergents (Eriksson 2002). The most common elements in
the gray water are Na, Al, and Zn. The Na concentrations in many of powder
detergents ranged from 200 to 700 mg/L (Handreck and Black 2002).
The common chemical contaminants from bathroom gray water include soap,
shampoo, hair dye, toothpaste, and cleaning products (Mohamed et al. 2013). These
substances represent a source for nitrogen; however, the high concentrations of
nitrogen in the gray water from urban regions might be due to pass urine during
bathing (Mohamed et al. 2014). Gross et al. (2008) indicated that the detergents
might also are source for boron which is one of the dangerous elements. The dispose
of gray water with boron effects negatively on the plants even in a small amount
because it was toxic. Ahmad et al. (2009) stated that the boron reduces the repro-
ductive growth of plant and leading failure of newly divided cells to enlarge.
Grey water Treatment by Filtration Systems
The bathroom gray water with nutrients and pathogenic organisms introduced from
several sources should be managed probably to avoid the creation of bad odors,
stagnant water, and breeding sites for mosquitoes, as well as to prevent the occurrence
of eutrophication in the natural water systems and reduce the health risk for human.
The filtration system is among several technologies used for the treatment of gray
water; the filter is defined as a device or an instrument used for removing of pollutants
from the liquid wastes. It used as a primary treatment for the wastewater or an
advanced process depends on the filtration media. The filtration system is consisted
of gravel filter medium, mostly crushed, hard limestone which is efficient for
removing lint, fats, hair, and grease (Allen et al. 2010). However, a specific filtration
system is required from removing soluble pollutants such as nitrogen and phosphorus
from the wastewater (Dunets and Zheng 2013). Mohamed et al. (2014) examined peat
filter media for the treatment of bathroom gray water. Based on the method that has
been used, the designed system exhibited a significant removal of BOD within
7–28 days; the removal percentage ranged from 52% to 74%. However, the multi-
component filters consisted of clamshell, steel slag, limestone, and sand occurred
98% of turbidity, 96.2% of TSS, and 80% of COD within 3 days.
Ceramic
The utilization of ceramic as filters becomes popular for water treatment system,
but most of the ceramic are being used for point of applications only (National
Academy of Sciences 2008). Ceramics have high biocompatibility, high resistance in
corrosion, high resistance in compression, and low electrical and thermal conduc-
tivities (Sáenz et al. 1999). The filtration made from the ceramic is a simple
technology which made by mixing of clay with organic materials locally and
sustainably sourced through burning process and leave small pores throughout the
filter (Wald 2012).
Ceramic is made from clay and it is widely used in the ceramic industries; the clays
have high ion exchange capacity and can adsorb certain anions and cations exchanged
for other anions and cations in an aqueous solution (Obaje et al. 2013). Oyanedel-
Craver et al. (2014) indicated that the impregnated clays which contain traces of
crystalline albite or crystalline pyroxene with silver compounds showed high adsorp-
tion efficiency for metal removal. One more property of the ceramic is the small pores
in the filter which can be used to remove small organism such as bacteria while the
colloidal silver acts as a chemical biocide to kill microbes (Wald 2012).
The ceramic filtration media used in the design of filtration system are illustrated
in Table 2. Erhuanga et al. (2014) studied the efficiency of ceramic water filtration
as medium to removal of microbes or other contaminants from water. The
study revealed that the efficiency removal reaches to 100% of the metals such as
Pb. Abiriga and Kinyera (2014) at Kampala, Uganda, stated that a double filtration
made from different mixture ratios of clay powder, fine sawdust, and powder of grog
removes E. coli by 100%. Nasir and Faizal (2016) found that the treatment system
using mixture of natural clay, rice bran, and iron powder to form ceramic filters
removed cadmium (Cd) by 99.0%. Subriyer (2013) indicated that the ceramic filter
from natural clay and fly ash can remove Fe and Zinc ions by 95%. Based on these
studies, it can be proven that ceramic water filter can remove the contamination of
54
Table 2 Efficiency of using ceramic in different treatment system

Greywater Pollutant
Researcher Location Greywater treatment system sources Particle size (mm) removal Advantages
Erhuanga Akure, Ceramic water filtration used of a porous Wells, – Lead Effective in the
et al. Nigeria ceramic (fired clay) as medium to filter boreholes, and (Pb) (100%) treatment of
(2014) microbes or other contaminants from stream Sulfate physiochemical
water (SO4) contaminants detected
(76%) in the water samples
Iron
(Fe) (47%)
Fluoride
(75%)
Abiriga Kampala, Double filtration on the rate of water Contaminated Ball clay mineral E. coli –
and Uganda percolation and E. coli removal efficiency water and hard wood (100%)
Kinyera of ceramic water filters (clay powder, fine sawdust (1 mm
(2014) sawdust, and powder of grog) sieves) to obtain
powder
Nasir and Indralaya, Ceramic filters made from a mixture of Pulp industry Natural clay (), Cadmium Effective in removing
Faizal Indonesia natural clay, rice bran, and iron powder in effluent rice bran (500 μm), (99.0%) cadmium
Treatment of Domestic Gray Water by Multicomponent Filters
(2016) removing cadmium iron powder

(500 μm)
Subriyer Sriwijaya Ceramic filter made of natural clay, fly Tap water 77.5% natural clay, Fe ions –
(2013) University, ash, and iron powder 20% fly ash, and (99%)
Indonesia 2.5% iron powder Zinc ions
(96%)
1347
water and wastewater. The efficiency of this material very surprised and hold the
potential to be valuable sources for this treatment in removing many of pollutants
from the wastewater.
Size and Surface of Media
The removal efficiency of the ceramic in the pollutant removal depends on the proper
choice of filter depth, sand type, sand size, and filtration (Abudi 2011). The smaller
grain sizes fill between the large grain sizes and make the sand easier for the filtration
process (National Small Flows Clearinghouse 1997). In contrast, the fine particles
might facilitate the breakdown of organic compounds and recovery of nutrients.
Torrens et al. (2009) stated that the effective desired pollutant removal depends on
particle size and distribution, conditions of influent water, quality of effluent, the
filtration rate, and dosing regime and resting period duration. Culp et al. (1978)
claimed that the separating suspended and colloidal impurity process of water takes
place from water through the filtration media material. The water fills the pore of the
filter medium, while the impurities are adsorbed on the surface or trapped in the
openings. Crites and Techobanoglous (1998) indicated that the filtration perfor-
mances of media characteristics are depending on effective grain size and coefficient
of uniformity. Thus, it affects the retention time of liquid or water and thus the
potential for clogging inside the pore surface of grains. The small material size has a
large surface area which might exhibit more efficiency for adsorption of particles and
adequate pore space which can promote aeration and unsaturated flow in media (Ball
1997). According to Erhuanga et al. (2014), ceramic used in the design treatment
systems are available in three sizes which are 1.18, 0.60, and 0.25 mm.
Conclusion
In a nutshell, this study provides a theoretical base for research and helps to
determine the nature of the research. This chapter may also serve as a handy guide
for ceramic filtration systems. For future studies, the extension of time should be
improved in order to identify the effectiveness of ceramic filter systems in the
removal of gray water contamination.
Cross-References
Kitchen Wastewater
Acknowledgments The authors gratefully acknowledge assistance provided under the contract
grant, FRGS vot 1453, to support our research needs.
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Development In-House: A Trap Method for
Pretreatment of Fat, Oil, and Grease in 55
Kitchen Wastewater
R. M. S. Radin Mohamed, Adel Al-Gheethi, A. N. Welfrad, and

M. K. Amir Hashim
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1352
Kitchen Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1354
Fat, Oil, and Grease (FOG) from Kitchen Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1354
Effects of Kitchen Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1357
Technology of FOG Trap Pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1357
Gravity Separators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1358
Electrocoagulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1358
Bioaugmentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1359
Model and Manufacture of FOG Trap Available in Market . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1359
Previous Studies Conducted on the Kitchen FOG Wastewater Treatment . . . . . . . . . . . . . . . . . . . . 1362
Challenge and Development of Interceptor for FOG in Malaysia . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1364
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1364
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1365
Abstract
Most of the commercial restaurant and domestic house kitchen does not equip
with the proper kitchen wastewater treatment. These wastes contain high concen-
trations of fat, oil, and grease (FOG) which are disposed into the sewerage
network and increase the sanitary sewer overflow (SSO). The present chapter
discusses the individual treatment systems which are used for the removal of FOG
from the kitchen wastewater. The most common and cheapest FOG treatment
system is by using the gravity separation. However, in order to increase the
efficiency of these systems, some of the researchers have been using natural
R. M. S. Radin Mohamed · A. Al-Gheethi (*) · A. N. Welfrad · M. K. Amir Hashim

Micro-pollution Research Centre (MPRC), Department of Water and Environmental Engineering,
Faculty of Civil & Environmental Engineering, Universiti Tun Hussein Onn Malaysia, Parit Raja,
Johor, Malaysia
e-mail: maya@uthm.edu.my; adel@uthm.edu.my

https://doi.org/10.1007/978-3-319-73645-7_35
materials to enhance the adsorption process of FOG. The establishment of a

reliable FOG treatment system for each house based on the separation system
might contribute effectively in the FOG removal concentration in the kitchen
wastewater.
Keywords
Fog · Kitchen wastewater · Removal · Individual usage
Introduction
Nowadays, fat, oil, and grease (FOG) blockage becomes a worldwide concern due to
their role in the increasing water pollution. According to American Environmental
Agency (USEPA 2004), 10,350–36,000 sanitary sewer overflow (SSO) cases are
occurring every year (Husain et al. 2014). In Malaysia, it has been estimated that the
total quantity of wastewater from municipal and industrial sectors which enter
sewerage systems is 2.97 billion cubic meters per year (Mat et al. 2012). Moreover,
the population growth rate in Malaysia is 1.5% (Labourforce Survey 2015). The
increasing of the population is associated with the increasing of the quantities of
the wastewater and thus the level of risk in terms of the severity of the problem and
the likelihood of the blockage of sewerage system. Therefore, a proper planning to
design and manage the FOG wastewater is required to maintain the sewer system
efficiency. Nonetheless, the high load of FOG in the wastewater treatment plant
reduces the efficiency of the sewage treatment process. For this reason, the Depart-
ment of irrigation and drainage (DID) in Malaysia provides a guideline for the FOG
trap, to ensure the entire restaurant kitchen equip with sufficient design of FOG trap
system. However, as a result of the absence of the awareness on the nature conser-
vation issue, most of the restaurants in Malaysia have not equipped with a proper
kitchen wastewater treatment unit to treat the FOG contents in kitchen wastewater.
The FOG trap represents one of the most effective pretreatment methods to
separate and remove FOG from the kitchen wastewater. There are many different
types of FOG trap that are available in the markets. In the Economic Transformation
Program (ETP) introduced by Malaysia Prime Minister in 2013, the grease trap
system upgrading work is only focusing in the Kuala Lumpur and Klang Valley. The
area is chosen because it is the country capital city to a world-class city and globally
competitive economic hub (Annual Report, Malaysia Federal of Governor of
the Federal Reserve System). High installation cost and operation and maintenance
cost lead the restaurant owner in the rural and suburban area to take least effort to
properly maintain the system.
FOG from kitchen wastewater receives the least concern in wastewater treatment,
especially for domestic and commercial pretreatment process. However, the
untreated kitchen wastewater that is discharged into the sewer trunk results in
sewer blockage and causes SSOs. The first process of kitchen wastewater treatment
at the restaurant is by sorting and removing the large debris such as the bone, food
waste, and kitchenware. The washing process of plate and kitchenware using
55 Development In-House: A Trap Method for Pretreatment of Fat, Oil, and. . . 1353
Fig. 1 Improper waste water pretreatment and filtration by a local restaurant in Malaysia (Photo
was taken on 10 November 2016)
Fig. 2 Drainage blockage due to kitchen wastewater (Photo taken on 10 November 2016)
detergent and water washes the FOG and the leftover food waste into the filtration
mesh screen. In some restaurant, the screening is conducted by using a plastic basket
with 3 mm of diameter which is able to screen a very few amounts of the kitchen
waste; meanwhile the fine debris and FOG contamination will flow into the drainage
sewer system without the proper filtration system (Fig. 1).
The observation made at the premise found that the drainage system is a drainage
blockage due to solidified FOG and the kitchen waste as shown in Fig. 2. The
improper FOG filtration system does not only result sewer blockage but also cause
the bad odor around the restaurant. Untreated kitchen wastewater disposal also leads
to the increase of the contamination load at the nearby river.
FOGs in wastewater create problems including the production of foul odors,

interference with proper operation of wastewater treatment works, and the blockage
of sewer lines leading to sanitary sewer overflows (SSOs). About 50% of SSOs
occur as a result of line blockings with the largest source at 47% of these blockages
attributed to FOG deposits that accumulate in sewer lines (US EPA 2004). SSOs can
potentially release high pathogens, nutrients, and solid loadings that result in harm to
public health and the environment. This chapter aimed to highlight and review the
previous kitchen wastewater treatment effectiveness used for the treatment of
kitchen wastewater.
Kitchen Wastewater
Kitchen wastewater is defined as a heavily polluted wastewater with food particles,

oil, fat, and grease. The FOG concentrations in the commercial restaurant kitchen
wastewater range from 50 to 2100 mg/L. These concentrations play an important
role in the growth of microorganisms in the sewer line and create odor for open
trench drainage (Chen et al. 2000). The solid food waste particles are combined with
the FOG molecule and result the FOG to harden and solidify, thus causing sewer
blockage. In the United States, FOGs are generated from commercial food and
beverage service establishments which are accumulated in sewer line systems in
the form of hardened solids and are responsible for approximately 50–75% of annual
sanitary sewer overflows (SSOs) (Ducoste et al. 2008). Kitchen wastewater sources
that discharge to the sewer system include garbage grinders, prewash sinks, prep
sinks, dishwashers, floor drains, tilt kettles, steam trays, floor sinks, floor drains, and
hood-cleaning residue.
Fat, Oil, and Grease (FOG) from Kitchen Wastewater
Domestic wastewater with high contents of organic matter is mainly derived from
kitchen wastes, which consisted of the remnants of vegetable oils and animal fats as
well as proteins and suspended solids. The composition of these wastes varies
considerably depending on the food restaurant activity that produces the different
types of food (Alves 2013). FOG is a term used to represent the lipid layer formed on
the surface of the wastewater generated from the cooking and food processing. These
FOGs might be accumulated on the pipe walls and form hardened deposits as a result
of the chemical reaction with the other chemical substances in the wastewater or due
to the physical aggregation process (He 2012a). The deposits are the main reason for
the reduction of conveyance capacity and the occurrence of sanitary sewer overflow.
The annual production of collected grease trap waste and uncollected FOG entering
sewerage treatment plants in the United States ranges from 350 to 7700 kg/year per
restaurant. EPA stated that the combined sewer overflow and sanitary sewer over-
flows FOG from homes and restaurants as well as from the industrial sources are the
most common reasons for sewer blockages. Grease is problematic when it solidifies
and affects the conveyance capacity and blocks the sewer line. FOG is presented in
the wastewater as liquid or solid substances and is characterized by a greasy texture
in its pure state. FOG is colorless, odorless, and tasteless. Moreover, FOG is soluble
in organic solvents such as ether, hexane, and chloroform but not in water (Husain
et al. 2014). Oils and fats are a subsection of lipids that are composed of fatty acids,
triacylglycerols, and lipid soluble hydrocarbons that are minor but important com-
ponents of FOGs. FOG has a density less than water (specific gravity is less than 1),
and thus, it floats on the water surface. However, FOG forms emulsions with
aqueous media in the presence of soap or other emulsifying agents. Gravity separates
free-floating oils from water because their specific gravities are less than 1. Petro-
leum-based oils typically can be removed from wastewater by skimming them off
the top of sedimentation basins. Kitchen wastewater is physically and chemically
polluted as it also contains detergent and cleaning agent, and where dishwashers are
used, the kitchen wastewater is in alkaline form. According to the Arizona depart-
ment of environment quality guideline, there are five types of oil that are found in the
wastewater (Hess et al. 2016). The most common type is free oil where oil is present
in water having little if no water associated with it and can be easily separated by
gravity separation method because the oil will rise rapidly to the surface of the water
tank under calm conditions.
Mechanically emulsified oil is categorized as oil dispersed in water in a stable
form as 20–150 μm droplets. It is stabilized by electrical charges and other forces
that result in the coating of suspended solids. Such oils mix with water due to shear
that can result from the wastewater travelling through a pump, wastewater splashing
into a tank, and anything that will break up and disperse larger oil droplets. Oil
dispersed in the water droplets less than <5 μm is called chemical emulsion formed
by detergents, alkaline fluids, chelating agents, or proteins found in the kitchen
wastewater. Dissolved oils solubilized in liquid are oils from the light end of the oil
spectrum such as benzene, toluene, and xylene. The molecules are less than five
microns in size, and so they are removed very effectively by activated carbon in
wastewater treatment. Oil-wet solids include oil that adheres to sediments and other
particulate matters such as metal chafing that are common in industrial wastewater.
The oil particle is not combining with the water particle but combines with the
kitchen food waste. This oil-wet solid is removed by using media filter, flocculation
process, filter bag, and FOG separator.
The characteristics of restaurant kitchen wastewater are illustrated in Table 1.
The wastewater analysis is then being compared to the Malaysia acceptable condi-
tions standard A and B with the set of wastewater quality requirement before
discharge into the water body. The parameter of wastewater analysis is pH, COD,
BOD, FOG, and TSS. Mohamed et al. (2013) conducted a sampling from the
residential kitchen and recorded a FOG value from 136 to 219 mg/L, which is
200% higher than the standard B (10 mg/L) required by the Malaysia Environment
Act 1974. The TSS values are slightly low compared to the research conducted by
Chen et al. (2000) at Hong Kong which was the highest value of TSS recorded at
student canteen (1320 mg/L). The study revealed that the FOG concentration was
1356
Table 1 Characteristics of kitchen wastewater from houses and restaurants compared with Malaysian standard for effluent discharge
Malaysia
(Mohamed Florida (Matejcek et al.
Researcher et al. 2013) Stockholm (Alves 2013) Hong Kong (Chen et al. 2000) 2000)
Residential Restaurant Restaurant 15
house Syster O Restaurant Guld Chinese Western American Student Restaurants restaurants Malaysia Malaysia
Restaurant kitchen Bror Brasilia Tuppen restaurant restaurant fast food canteen UC bistro in Florida in Florida acceptable acceptable
Number of conditions conditions
samples 12 90 90 90 10 10 11 14 3 NR 109 standard A standard B
pH 4.2–4.7 5.52–6.35 4.88–5.73 6.04–6.94 6.62–7.96 6.94–9.47 6.30–7.23 6.82–8.76 6.03–8.22 NR NR 6.0–9.0 5.5–9.0
COD 124–149 1400–2100 1300–2200 820–1400 292–3390 912–3500 980–4240 900–3250 1500–1760 NR NR 120 200
mg/L
BOD 67–88 920–1500 720–1200 490–740 58–1430 489–1410 405–2240 545–1630 45 1–704 441–1920 53–1009 20 50
mg/L
FOG mg/L 136–219 210–560 140–520 110–240 120–172 52.6–2100 158–799 415–1970 140–410 18–83 5–196 5.0 10.0
TSS mg/L 212–312 430–760 160–620 69–330 132–246 152–545 68–345 124–1320 359–567 43–454 9–268 50 100
R. M. S. Radin Mohamed et al.
found highest at the western restaurants with 2100 mg/L, probably due to high
consumption of vegetable oil in cooking and food preparation. The study performed
at Stockholm in three different restaurants showed that a variation of data of FOG
concentrations due to the different types of food menu style variation, FOG ranged
from 110 to 560 mg/L, which considered as highly contaminated (Alves 2013).
Matejcek et al. (2000) indicated that the lowest concentration of kitchen wastewater
discharge at Florida was between 5 and 83 mg/L. FOG concentrations are dependent
on the type of the restaurant; the vegetarian restaurant produced less FOG in their
kitchen wastewater compared to the BBQ and grill restaurant which used a large
volume of meat and cooking oil.
Effects of Kitchen Wastewater
FOGs are the most common pollutants which cause the sewer blockage. It has found
that 70% of the sanitary sewer overflows (SSOs) in Malaysia were recorded as a
result of FOG. In 2010, the Indah Water Konsortium (IWK) has received 22,184 of
blockage inquiries (IWK 2017). Increasing of the blockage case increase the block-
age clearing cost that bears by the municipal council. The FOG in a liquid form may
be less harmful, but once the FOG get cool in the sewer line, they congeal and
harden, making it toxic and which stick to the inner lining of sewer pipe restricting
the wastewater flow and causing blockage which is costly for maintenance work by
the municipal authorities. Blockages in the wastewater collection system are serious,
causing sewage spills, manhole overflows, or sewage backups in homes and busi-
nesses (He 2012b).
Among water pollution sources, kitchen wastewater has high oil and grease
contents. In many developing countries, most of the kitchen activities often dis-
charge the polluted water flow into rivers and stream without treatment (Mohamed
et al. 2013). Untreated kitchen wastewater causes a eutrophication phenomenon if it
enters ponded surface water in large enough quantities. Furthermore, the stagnant
kitchen wastewater can become anoxic and create unpleasant odor by the release
nutrients such as ammonia as well increase the possibility of sewer blockage.
Technology of FOG Trap Pretreatment
The grease trap and grease interceptors (GIS) are kitchen grease separation devices
with different quantities of the wastes (200 and 3000 L, respectively) (Engle 2006).
In these treatments the designed devices are installed closely to the source of FOGs
which are separated from the kitchen wastewater before the discharge into the
downstream treatment units. In the GIS system, the devices are installed between
wastewater effluent points and the sewer system to allow FOG to be trapped. In
contrast, the designed FOG trap can be removed freely and dispersed FOG by
gravitational separation (Nisola et al. 2009). The free (non-emulsified) FOG is
separated mechanically as a response for the gravity separation because they are
floated and agglomerated on the surface of wastewater. However, the emulsified

FOG is the main challenge, because they are suspended within the wastewater;
therefore, the emulsified FOGs require analytical enzymes or chemical substance to
react and cause the FOG to coagulate and participate in the bottom of the FOG
retention chamber. Nowadays, there are several types of domestic pretreatment system
that is used for separation of FOG. The most common FOG trap is based on the gravity
separation, chemical enhanced separation process, as well as conventional filtration
and ultrafiltration processes. Different types of FOG trap have different effectiveness.
Gravity Separators
Gravity separators are used for small packaged restaurant units or the large commer-
cial industrial product recovery systems. The first stage of the treatment system is an
oil interceptor (grease trap), which is used at commercial establishments with small,
intermittent discharge quantity of FOG (e.g., restaurants, hotels, and service stations).
In some kitchens, they are used small units which often include a mechanical oil
skimming device, while the large grease traps are designed for external installation
and are often installed under the ground or in the drainage system between sink or
floor drains and the building sewer. In the food industry, with the high quantities of the
discharged oils, it is reused as animal feed (Water and Sdn 2010).
Gravity separation acts based on the flotation/gravitational separation which is
more efficient for separation of suspended matter (Alves 2013). The major flow
changes play an important role in the removal efficiency; therefore, the flow equal-
ization installation is required to avoid the problem. The hydraulic capacity, flow
configuration, cleaning ease, and convenience are the main points which should be
considered by engineers. The distance between the trap’s inlet and outlet should be
sufficient to prevent grease from escaping via the outlet.
Electrocoagulation
Electrocoagulation is one of the most efficient technologies for the treatment of

urban wastewater, oil shale wastewater, and oil–water emulsion. The technology has a
fast rate of pollutant removal, simplicity in the operation, compact size of the equip-
ment, as well as low capital and operating costs and has achieved 94% of the oil and
grease removal from the wastewaters tested (Chen et al. 2000). It is applicable for the
removal of small and light suspended particles from the kitchen wastewaters, due to
the accompanying electro-flotation effect which increase the FOG treatment process.
The schematic diagram of electrocoagulation unit is shown in Fig. 3; it consists of an
electrochemical reactor and a separator unit. Kitchen wastewater flows upward in the
electrochemical reactor and downward in the separator. The unit is consisted of five
electrodes made up of aluminium and iron which are connected in a dipolar mode. The
effective contact area of each electrode is 56 cm2, and the spacing between electrodes
is 6 mm. A stirrer is employed in the feed tank to maintain an unchanged composition
Fig. 3 Schematic diagram of

experimental setup.
(1) Magnetic stirrer; (2) feed
sludge tank; (3) pump;
(4) electrochemical reactor;
(5) separator; (6) DC power
supply (Adapted from
Storm water Management
Incelectrocoagulation
system (EC))
of the feeding wastewater due to settlement of the kitchen wastewater solid waste and
FOG. The optimal density between 30 and 80 A/m2 is while charge loading ranging
from 1.67 to 9.95 F/m3 with less than 1.5 kW h/m3 of the power.
Bioaugmentation
Bioaugmentation is a biological technology that introduces a selected microorgan-

ism that has the ability to produce hydrolysis enzymes such as lipase to improve
FOG degradation in the wastewater (Alves 2013). This microorganism used the
FOG as a carbon source; thus it has the ability to grow and multiply in the
wastewater with FOG. In some case a consortium of bacteria are used for achieving
high removal process (Al-Gheethi et al. 2017). The potential of selected bacterial
species for degrading of lipids by lipolytic enzymes has been reported in the
literature (Treichel et al. 2010). The bioaugmentation process has been used for
treating different types of wastewater (Al-Gheethi et al. 2016).
Model and Manufacture of FOG Trap Available in Market
Throughout the research and development toward sustainable water management

systems and decentralized residential and commercial kitchen wastewater treatment
technologies, many companies try to come up with the latest and highly efficient
wastewater filtration equipment. The competition among the manufacture in terms of
energy efficiency and economic type of FOG trap has expanded to the international
market. Moreover, some of the current directions aimed to produce biodiesel from
the used cooking oil (Husain et al. 2014). The FOG traps which are available in
today market are presented in Table 2. It can be noted that there are different designs
for FOG trap, while the maintenance cost is varied depending on the filter medium
or the material used in the treatment process.
Table 2 FOG trap available in market and the efficiency in removal percentage of FOG
No Fog trap model Description Comment
1 Type: FOGHog This design is This design no
Manufacturer: BioMicrobics made of 100% need for energy,
Operating type: gravity separation corrosion-resistant and easy
polyethylene. It implement,
can remove 95% maintenance and
of solids and clearance for
grease from the internal parts
kitchen
wastewater. This
design can be
installed under the
counter or prior to
a treatment system
inflows ranging
from 75 to 378 L/
min and is more
suitable for
commercial
kitchens of
restaurants,
cafeterias, motels,
hotels, and/or other
institutions where
food is prepared
2 Model: Goslyn GOS Xx-X series The exterior More suitable for
construction is restaurant with
made of stainless continuous
steel operations (24 h)
Manufacturer: Goslyn LP (Texas, USA) Has the efficiency The capacity is
to filter 99.6% of 100 gallons/min
FOG
concentrations
Operating type: filter media (membrane Has a strainer Need an energy to
filtration) basket to prevent operate
solid debris from
entering the drain
pipes
Has two oil
collection
cassettes
(continued)
Table 2 (continued)
3 Model: Trapzilla supercapacity grease trap Can be installed Easy
manufacture: aqua mundus (UK) on the floor or in implementable
ground outside
the facility
Operating type: gravity separation The capacity is High installation
2.21 L/ps flow cost
and stores 72 kg Need a large area
of grease for installation
4 Model: aqua bio-pro Automatically Provide a free oil

operating wastewater into
the drains
Manufacture: aqua mundus (UK) Small system Treatment for fats,
sizes thus can be oils, and grease by
fixed in a the degradation
unrestricted process
location
Operating type: bioaugmentation Depend on the Contribute in the
special strains of reduction of odors
bacteria which is produced from the
the most efficient drains
for the Environmentally
degradation of friendly as the
lipids process used is a
biological a
process
Easy installation
5 Model: aqua Bio-ProBig dipper system Automatic Contribute in

operation and preventing the
self-cleaning drainage
cycle blockages and
odors
Manufacture: aqua mundus (UK) Made of Remove
corrosion- incidental food
resistant materials solids by
filtration
(continued)
Table 2 (continued)
Operating type: filter media Has an integrated
motor/grease
outlet/heater/lid
enables easily
handed
installation
Has 98% of the
removal
efficiency
Previous Studies Conducted on the Kitchen FOG Wastewater

Treatment
The previous studies conducted on the kitchen fog wastewater treatment are pre-
sented in Table 3. These studies aimed to determine the efficiency of pretreatment
process in FOGs from the kitchen wastewater. The media filter method is the most
economical compared to the other method since the ultrafilter, bioaugmentation, and
electrocoagulation require a special operation and material to operate. The soil filter
was able to remove 30–95% of FOG concentration based on filtration process.
Mohamed et al. (2013) measured the efficiency of wastewater treatment using
peat soil as filter media. The study revealed that the concentration of FOG reduced
by 80–88%. Alves (2013) used GOR BioSystem; the effectiveness of the filtration
recorded only 22% for FOG. The ultrafilter method used by Kim et al. (2002)
achieved high removal of FOG up to 98%, which indicates that the ultrafiltration
has the potential to reach high-level purification of wastewater. However, this
technology requires high cost for the maintenance to supply the filter medium and
requires an advance system to operate. Electrocoagulation pretreatment method
examined by Chen et al. (2000) removed 94% of FOG concentrations from the
wastewater.
Table 3 Removal efficiency of FOGs from kitchen wastewater by the pretreatment system
Removal
Residential/ efficiency Suitability/
References Location commercial Treatment (%) advantages
Mohamed Batu Pahat Residential Peat filter 80–88 Inexpensive of
et al. (2013) Malaysia Application of peat filtration
filter media to filter method
the FOG depending on
concentrations the soil particle
size
Alves (2013) Stockholm Commercial Bioaugmentation 22 Ineffective
Sweden method of
wastewater
treatment
Using GOR Expensive to
BioSystem in maintain the
kitchen wastewater system
pretreatment operation
process
Water Stockholm, Residential Soil filter: 30–95 Soil not to
Environment Sweden Water percolate coarsely or
Federation though the soil in finely purify
(2005) the small pores, depending on
leaving the bigger the soil particle
pores open and and soil
aerated to allow chemical
gas exchange characteristic
Kim et al. Incheon, Residential Ultrafilter: 90–98 Expensive to
(2005) South maintain
Korea Consist of feeding Low energy
tank, permeate consumption
reject handling High level of
facilities, purification
monitoring, and
control unit. Based
on cross flow
filtration
Chen et al. Hong Kong Commercial Electrocoagulation 94 Feasible
(2000) process for
Different electrode Treating the
materials and kitchen
operational wastewater
conditions were Required
examined. continuous
Aluminum was electric supply
preferred to iron to operate
Challenge and Development of Interceptor for FOG in Malaysia
The lacks of awareness about the problem associated with the direct dispose of
FOG into the stream represent the main challenge part to solve this problem due to
the absence of regulations for the discharge of kitchen wastewater into the drain.
Grease traps should be installed at each restaurant and food processing establish-
ment to separate the cooking oils and animal fats from sewage flow. According to
MOH’s Water Supply & Environmental Sanitation Program in Malaysia, Annual
Report 2011, the main challenges include the low sewerage tariff which is unable
to support the high FOG trap operation and maintenance costs. Environment
Quality Act (EQA) 1974 has stated that the FOG effluent discharge must be less
than 10 mg/L for standard B for inland waters or Malaysian waters and 5 mg/L for
standard A where the discharges into any inland waters within catchment
areas listed in the Third Schedule. However, the non-compliance of treated sewage
for the national standards are mainly due to the high influent of FOG discharged
into STPs from the serving industrial and commercial areas and food-related
business premises that do not have grease traps installed or do not maintain grease
traps adequately to maintain filter or purification efficiency. Sewerage service
collection by operators is not conducive as it is unfortunate that many Malaysians
fail to realize the importance of sewage management with regard to a safer
environment.
Conclusion
The weakness of existing grease trap of FOGs is the main reason for sewer blockage
issue. The loss of productivity and operation of the restaurant is due to sewer
blockage which can be avoided by developing an in-house pretreatment method of
FOG interceptor for kitchen wastewater discharge. The most suitable FOG trap to be
established is gravity separation method with application of automatic in removing
the filtered FOG to minimize the maintenance work of FOG trap. Future develop-
ment and research are needed to establish an efficient and low cost in terms of
installation, operation, and maintenance. The new development of FOF trap might
allow for the FOG trap to be installed in every food commercial and residential user.
Thus, this may reduce the financial load on the maintenance and repair cost by the
municipal authorities in solving the blockage issue caused by the high concentration
of FOG in the sewer line.
Cross-References
▶ Microbial Risk Associated with Application of Biosolids in Agriculture

▶ Removal of Pharmaceutically Active Compounds from Contaminated Water and
Wastewater Using Biochar as Low-Cost Adsorbents, An Overview
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Environmental Treatment
Technologies: Adsorption 56
Subramanyam Busetty
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1368
Principles of Adsorption: Concepts and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1368
Historical Aspects of Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1369
Theory of Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1369
Rate of Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1370
Adsorption Versus Other Separation Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1370
Biological Treatment Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1370
Steam Stripping Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1371
Enzymatic Oxidation Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1371
Reverse Osmosis Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1372
Solvent Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1372
Catalytic Oxidation Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1372
Non-Conventional Adsorbents for Water and Wastewater Treatment . . . . . . . . . . . . . . . . . . . . . . . . . 1373
Zeolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1373
Siliceous Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374
Biosorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1375
Soil as Adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1376
Agriculture and Industrial Residue/By-Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1377
Carbons Prepared from Residues/Wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1377
Industrial Solid Waste (By-Products/Waste Materials) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1378
Agro-Residue as Adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379
Correlation and Estimation of Performance of Adsorption Systems . . . . . . . . . . . . . . . . . . . . . . . . . . 1380
Isotherm Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1381
Estimation of Best-Fitting Isotherm Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1386
Error Functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1386
Statistical Functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1387
Kinetic Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1387
Adsorption Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1387
Pseudo-First-Order Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1388
S. Busetty (*)
SASTRA Deemed University, Thanjavur, India
e-mail: subramanyamjy@gmail.com

https://doi.org/10.1007/978-3-319-73645-7_37
1368 S. Busetty
Pseudo-Second-Order Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1388

Elovich Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1389
Thermodynamic Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1389
Fundamentals of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1389
Column Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1390
Fixed-Bed Adsorption Column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1390
Bed Depth Service Time (BDST) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1391
Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1392
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1393
Abstract
In the field of environmental engineering, adsorption plays an integral role among
methods to treat contaminants because of its robustness in handling a range of
pollutants as well as its simplicity in operation. This chapter provides the basic
principles underlying adsorption technology and the effect of several aspects,
specifically pH, adsorbent dosage, and contact time in optimizing the adsorption
capacity of an adsorbent (the material that adsorbs) towards the adsorbate (that
which is adsorbed). The methods of modeling the adsorption data, with varying
degrees of freedom, for isotherm, kinetic, and thermodynamic as well as column
studies are presented with illustrative results, along with their significance in
designing a fixed-bed adsorption unit. A synoptic understanding of the most
commonly used adsorbents (both conventional and nonconventional), their ana-
lytic characterization as well as applicability with regards to various wastewater is
also provided. Finally, a short outline of regeneration and desorption methods as
well as operational and maintenance considerations is presented.
Keywords
Adsorption · Separation technologies · Isotherm model · Biodegradation
Introduction
Biodegradation is the utmost significant tool for the total removal of pollutants from
the environment. It is natural way of attainment of wastes by breaking down organic
matter into nutrients that can be used by other organisms. As a result, the ability of
pollutants to biodegrade is a crucial in the understanding of any risk posed by those
pollutants on the environment.
Principles of Adsorption: Concepts and Applications
Adsorption, one of the simplest, safest, and most cost-effective (and, possibly,
environmentally friendly subject to the degree of regeneration/bioremediation) tech-
niques for removing contaminants from the environment, is being studied widely
(both for removal of phenolic as well as non-phenolic materials), especially with
regard to evaluation of the relationship between adsorption capacity and adsorbent
56 Environmental Treatment Technologies: Adsorption 1369
characteristics of different types of adsorbent–adsorbate systems. Some of the most

commonly used adsorbents include modified clays, commercial activated carbon,
as well as activated carbons derived from other materials (such as dates, rice husk,
lemon peel, etc.) to remove a wide range of pollutants (such as phenol, heavy metals,
etc.). However, the use of a soil–agro residue blend, which is the very objective
of the present project work, does not appear to have been reported before. The
following is a brief thematic survey of the literature.
Historical Aspects of Adsorption
The need for synthesis of new adsorbents for industrial requirements has enhanced
adsorption technology. Adsorption technologies have their origins in earlier discov-
eries – the theoretical concepts, experimental results, and terminology concepts of
adsorption date back several decades. Probably the first quantitative observations of
adsorption of gases by charcoal and clay were carried out by Scheele in 1773 and
Fontana in 1777 (as referenced in Dabrowski 2001). According to Lowitz, the
modern applications of adsorption were carried out to decolorize tartaric acid
using charcoal (as referenced in Dabrowski 2001). In 1814, de Saussure carried
out systematic studies of adsorption of gases using porous materials (sea foam, cork,
charcoal, and asbestos) and he also discovered that the adsorption process is
exothermic in nature (liberation of heat). In the nineteenth century, Chappuis,
Joulian, and Kayser published a number of research papers. Chappuis carried out
his experimental work at a constant temperature, studying the adsorption of ammo-
nia on charcoal and asbestos. He also studied adsorption of sulfur dioxide, carbon
dioxide, and air on charcoal at different pressures of the gases.
Kayser introduced the term adsorption in the adsorption science and technology
literature, but it was first proposed by du Bios-Reymond. Kayser also introduced the
terms isotherm and isotherm curves at constant temperature as well as the basic
concepts of monolayer adsorption theory. Later on, isotherm equations were used to
discover the characteristics of adsorbents (such as pore size, pore volume, energy,
surface area, pH, concentration, etc.). Based on this information, specific adsorption
isotherm curves were developed and used to understand the relations between different
properties of adsorbent and adsorbate materials. In order to correlate experimental data
relating to adsorption, isotherm is expressed in terms of isotherm models. The models
derived were based on experimental data, and following this model assumptions were
proposed. These models (experimental results) and assumptions were then used to
develop adsorption process theory. The theory developed can help as a guide for new
experiments to test the experimental results. Adsorption science and technology has
developed via an ongoing interplay between theory and experiment.
Theory of Adsorption
Adsorption is a process in which contaminants are transferred from a solution to the

surface of a solid (adsorbent) through physical/chemical forces (physio-sorption/
chemisorption). In physio-sorption, due to the Van der Waals force of attraction
1370 S. Busetty
between the adsorbate and number of sites available on adsorbents, the adsorption
may occur in mono- or multi-molecular layers, often accompanied by capillary
condensation within the pores. In fact, by decreasing the pressure and increasing
the temperature, the phase of the adsorption is altered. Thus, this process is quite fast
and reversible. The second type of adsorption is chemisorption; this involves valence
forces available on the surface of the adsorbent. Exchange of atoms therefore takes
place between the adsorbent and adsorbate Chemisorption is more favorable at
higher temperatures than lower temperatures, while physio-sorption works well at
lower temperatures. The chemisorption process is much slower than physical
adsorption because of the exchange of atoms that must occur in the molecules.
Chemisorption is an irrevocable and endothermic process and is typically limited to
a single layer of adsorption (Sing 1989). The adsorption process affects the interac-
tion between adsorbent and adsorbate and also depends on the solution pH, concen-
tration, temperature, molecular weight, molecular size, structure, and polarity
(Ahmedna 1998). A third force of attraction is the electrostatic force between ions
and charged functional groups available on the surface of the adsorbents. This
process is called ion exchange (as referenced in Ahmedna 1998).
Rate of Adsorption
If a nonporous, adsorbent particle surface is exposed to fluid adsorbate, the adsorp-

tion of the adsorbate consists of several steps for transporting the adsorbate from the
bulk phase on the interior particle surfaces as well as for its adsorption onto the
particle sites. The following mass transfer process may take place: inter-particle
mass transfer, inter-phase mass transfer, and intra-particle mass transfer.
Inter-particle mass transfer refers to the diffusion, inter-phase mass transfer is
the transfer of adsorbate across the fluid particle interface, and intra-particle mass
transfer refers to the diffusion of adsorbate within the particle. Intra-particle mass
transfer often takes place simultaneously with adsorption.
Adsorption Versus Other Separation Technologies
Wastewater treatment is a process used to convert and make wastewater harmless or

suitable for reuse. The most common wastewater treatment methods are biological
processes, steam stripping, enzymatic oxidations, reverse osmosis, solvent extrac-
tion, catalytic oxidation, oxidation by H2O2, ionizing radiation, ozonation, and
adsorption/ion exchange.
Biological Treatment Methods
Biological treatment is one of the oldest treatment methods used for removal of toxic
and refractory compounds present in contaminated water and wastewater. With a few
exceptions, most organic compounds can be biodegraded, but in some cases the
biodegradation rate may be slow and required unique environmental conditions (i.e.,
start-up time, redox potential, pH, temperature, etc.,) (Metcalf and Eddy 2005).
Biological treatment methods are classified into two categories: aerobic and anaer-
obic treatment. Treatment of contaminated water and wastewater by biological
methods is probably the most efficient and cost-effective method (Cheremisinoff
1990; Mahajan 1994). Although aerobic biological treatment is predominant, the
anaerobic method is finding ever-increasing applications due to its low-energy
consumption and low sludge production (Ross 1989). Hickman and Novak (1984)
studied the ability of an activated sludge reactor to withstand the shock loads of
phenol, achieving 95% removal. The bacteria (Pseudomonas putida) are able to
degrade phenol into methane and CO2. The microbes proficient at degrading toxic
pollutants present in water and wastewater are extremely focused and need a
controlled, stable environment. To degrade mature biological sludge the microbes
require several weeks to acclimatize in ideal conditions, which include factors such
as temperature, pH, nutrients (nitrogen, phosphorus, and minerals), oxygen concen-
tration, toxicity, shock loading rates, and other organic concentrations in the water
and wastewater. The variations in any of the earlier parameters affect the equilibrium
conditions of the existing system. The efficiency (ranging from 65% to 90%) of the
microbiological system depends on the particular wastewater treatment system as
well as the capability to control the process parameters listed above.
Several researchers have studied removal of phenol by biological treatment
through use of the bench scale and pilot plants. Ehrhardt and Rehm (1989)
immobilized the bacteria onto activated carbon, resulting in it degrading up to
17 g/l in batch culture in 218 h. The extensive study of phenol degradation by
Arutchelvan et al. (2005) using Bacillus brevis was found to have a maximum
removal of 1750 mg/l within a period of 144 h, and Serratia marcescens was
found to be efficient in phenol degradation of up to 2000 mg/l in 6 days.
Steam Stripping Method
Steam stripping is one of the fast methods for removing phenol from contaminated
water and wastewater. In this method, dephenolation takes place at 100 C and
stripped phenol is absorbed by a 15% sodium hydroxide solution. It is estimated that
1000 m3 of wastewater would require 200 t of steam and 2 t of sodium hydroxide.
This method is useful for concentrations above 100 ppm of phenolated wastewaters,
but the capital cost of this method is high (Mahajan 1994).
Enzymatic Oxidation Method
Enzymes are biological catalysts, which speed up the reaction rate 1 million times
(Bailey and Ollis 1986). The enzyme catalyzed reaction for phenolic wastes may be
expressed as follows:
1372 S. Busetty
H2 O2 þ 2 ArOH ! 2 AR O þ 2 H2 O (1)
where ArOH is the phenolic waste and ARO is a phenoxy radical, which is highly
reactive and develops an insoluble polymer that can be removed by filtration. High-
strength phenol wastes are treated by the enzyme Caprius Macrorhizus Peroxidase
by an extra cellular peroxidase developed from common dung and fungus. The
soybean hull peroxidase is capable of oxidizing aromatic hydrocarbons in the
presence of hydrogen peroxide (Colin 1998).
Reverse Osmosis Method
Fang and Chian (1975) examined the split-up of polar organic compounds from water
using 12 various reverse osmosis membranes with 13 low molecular weight polar
organic compounds involving different functional groups. A series of membranes called
NS 200 membranes were reported to have the highest removal efficiency for phenol and
hydroquinone compared with the remaining 11 membranes. NS 200 membranes were
able to separate 85% of the phenol from the aqueous solution. Other researchers studied
phenol removal using a permeable polyamide membrane and reported a removal
efficiency of 78% of phenol for the optimum phenol concentration (Yanic et al. 1996).
Solvent Extraction
Solvent extraction is a frequently used method for removal of pollutants from

wastewater.
Solvent extraction for phenol is used especially when the phenol concentration is
high in the solution (Mahajan 1994). Examples of commonly used solvents are
benzene, light tar oil, hydrogenated tar oils ester groups, and phenosolvan (higher
partition coefficient than benzene). Once extracted the pollutant is washed out with a
caustic solution to form the sodium salt and the solvent is reused.
Depending on the type of industry, different solvents are used; in the petroleum
industry light catalytic oils are used and in the coking industry coke oven light oils
are used.
The extraction methods are uneconomical if the flow rates are lower than 200 and
350 m3/day in the benzene–NaOH method and phenosolvan method, respectively,
for a minimum phenol concentration of 2000 ppm (Mahajan 1994). Das (2000)
studied solvent extraction of Indian coals and the use of residual coals for solvent
extraction. The solvents ethylene–diamine and quinoline were reported to have
β-naphthol, p-nitrophenol, 2-chlorophenol, and phenol extraction comparable with
the phenol sorption by activated carbon.
Catalytic Oxidation Method
Catalytic oxidation is one of the most well-established techniques that permit

the decontamination of hazardous materials at a temperature less than 200 C and
pressure less than 100 bars using dynamic oxidation catalysts (Matatov-Meytal and
Sheintuch 1998; Imamura 1999). Studies on the aqueous-phase oxidation of phenol,
4-nitrophenol, 2-chlorophenol, and t-butyl alcohol in the concentration range of
2–5 g/l resulted in almost 100% elimination within a period of 100 min.
Non-Conventional Adsorbents for Water and Wastewater

Treatment
Attention has been focused on various natural solid materials that are able to remove
the pollutants from contaminated wastewater at a low cost. Cost is actually an
important parameter for comparing the adsorbent materials. An adsorbent can be
considered low-cost if it requires little processing, is abundant in nature (Bailey et al.
1999), and is a by-product or waste material from industry. Many researchers have
tested different waste products from industry, naturally available materials, and
agricultural process and proved them to be potentially economical alternative
adsorbents.
Zeolite
Zeolites are porous crystalline aluminosilicates that comprise assemblies of SiO4

and AlO4 tetrahedra joined together through the sharing of oxygen atoms. More
than 40 kinds of zeolite crystals have been found in natural mines and many types
can be synthesized industrially. Due to their adsorptive applications, zeolites are
widely using as alternative adsorbents. Intensive studies have been carried out
regarding removing pollutants from the water and waste waters.
Adsorption of surfactants and phenolic compounds was investigated by Kawai
and Tsutsumi (1995), modifying Na-Y zeolites using SiCl4.
Clinoptilolite is a natural zeolite that has been investigated by Sismanoglu and
Pura (2001) who studied the effect of adsorbate concentration and temperature for
removal of o-, m-, and p-nitrophenols. The activation energies (Ea) of nitrophenol
adsorption onto zeolite were estimated using the Arrhenius equation. The small
values of Ea for o- and m- nitrophenols indicates that intra-molecular hydrogen
bonding occurs and the surface of the molecule is smaller. Thus, it can be stated that
lower amounts of o- and m- nitrophenols are adsorbed on the surfaces of zeolite than
p-nitrophenols. Khalid et al. (2004) investigated removing phenol from an aqueous
solution in the concentration range of 0.1–1.6 g/L. The adsorption of phenol onto the
zeolite depends on the Si/Al ratio. At a high silica/alumina ratio the adsorbent has a
high adsorption capacity (hydrophobic). At lower phenol concentrations the adsorp-
tion of phenol onto the zeolite is more than that of activated carbon. In addition,
β polymorph A (BEA) zeolite was able to regenerate without affecting the original
properties. Kobeissy et al. (2008) have studied the hydrophobic Faujasite (FAU)
zeolites on various nitrophenolic compounds (ortho-nitrophenol [ONP], para-
nitrophenol [PNP], meta-nitrophenol [MNP], and 2,4-dinitrophenol [2,4-DNP])
from aqueous solutions. The adsorption capacity of the adsorbent depends on the
1374 S. Busetty
pH and solute solubility. It was also observed that ONP was adsorbed more easily
than the other components present in the binary mixture and the order of the
adsorption capacity of nitrophenolic compounds was reported to be as follows:
ONP > 2.4-DNP > PNP > MNP. The final conclusion is that hydrophobic FAU
zeolite is a good adsorbent and can be easily regenerated (Kobeissy et al. 2008).
BEA (β) and Zeolite Socony Mobil-5 (ZSM-5) zeolites as adsorbents for removal of
phenol and the performance of the adsorbents was compared with activated carbon,
studied by heat-flow micro-calorimetry. The values obtained of heats evolved during
phenol adsorption indicate the heterogeneity of active sites present on the investi-
gated systems for the adsorption of phenol. The equilibrium adsorption isotherm
data were interpreted using Langmuir, Freundlich, Dubinin-Astakov, and Sips’
equations. The Sips equation was found to express a high level of agreement with
experimental data. The results reveal that the adsorption of phenol on zeolites
depends on both the Si/Al ratio and pore size. Hydrophobic zeolites that possess
higher contents of Si show higher affinities for phenol adsorption. Among two
zeolites, zeolite β possesses the highest capacity for adsorption of phenol
(Damjanović et al. 2010). Using natural attapulgite and zeolite, a nano-structure
adsorbent was manufactured, namely attapulgite–zeolite composite, and used as
adsorbent for removal of phenol, and it was concluded that these zeolites are good
adsorbents (Wang et al. 2010).
Siliceous Materials
Natural siliceous materials such as bentonite and perlite have been utilized as
adsorbents to remove phenol from an aqueous solution (Koumanova and Peeva-
Antova 2002). The study investigated the effect of initial adsorbate concentration
and adsorbent mass on adsorbent using the batch adsorption experiments. The
adsorption equilibrium of p-chlorophenol (p-CP) on bentonite and perlite was
described by the Langmuir and Freundlich models. A higher adsorption capacity
was observed for bentonite (10.63 mg g1) than for perlite (5.84 mg g1). The
kinetic results reveals that among the adsorbents studied HiSiv 1000 has the highest
adsorption capacity. The effect of particle size, temperature, and thermal regenera-
tion were also studied on adsorption of phenol onto HiSiv1000. The adsorption
capacity decreased by increasing the particle size and adsorption capacity decreased
with increasing temperature. The effect of a mesoporous molecular sieve (M) Al-
MCM-41 (M = Na+, K+, Cu2+, Cr3+) was examined with regards to the adsorption
capacity of chlorinated phenol at a temperature ranging from 303 to 323 K. Different
isotherm models were studied to determine the best fit of the curve and the
Freundlich model was found to be the best fit. The adsorption capacity of penta-
chlorophenol (PCP) increased in the order (K) Al-MCM-41 < (Cr) Al-MCM-
41 < (Na) Al-MCM-41 < (Cu) Al-MCM-41. The isosteric analysis was carried
out on all the specified adsorbents, but (Cu) Al-MCM-41 and (Na) Al-MCM-41
presented a heterogeneous profile, whereas (K) Al-MCM-41 and (Cr) Al-MCM-41
did not (Marouf-Khelifa et al. 2004). Chitosan-coated perlite (CCP) beads, which
contain 23% chitosan, were used as an adsorbent for removal of phenolic com-
pounds (phenol, 2-chlorophenol, and 4-chlorophenol) by Kumar et al. (2010). Batch
and column flow experiments were conducted to determine the adsorption capacity
of the beads and the effect of different parameters, and isotherm models and kinetic
models were studied to identify the adsorption capacity as well as the rate of reaction
of the adsorbent. The experimental data best fits the Langmuir model and pseudo
first-order kinetic model.
Biosorbents
Biosorption occurs due to a number of metabolism-independent processes (phys-

ical and chemical adsorption, electrostatic interaction, ion exchange, complexa-
tion, chelation, and micro-precipitation) that essentially take place in the cell wall,
where the mechanisms responsible for the pollutant uptake will differ according to
the biomass type (Vijayaraghavan and Yun 2008; Aksu 2005). The main advan-
tages of biosorption are high selectivity and efficiency, cost effectiveness, and
good removal performance. Biosorbents mainly come under the following cate-
gories: bacteria, fungi, algae, industrial wastes, agricultural wastes, and other
polysaccharide materials. Raw materials such as seaweeds or wastes from other
industrial operations (fermentation wastes, activated sludge process wastes) can
also be used as biosorbents. Their performances are often comparable with those
of ion exchange resins.
Biosorption is a method of fast and reversible binding of pollutants from
water and wastewater onto functional groups that are present on the surface of
biomass. Tsezos and Bell (1989) observed that the uptake of PCP was found to
be adsorbed more by dead cells of Rhizopus arrhizus (4800 μg/g) than the live
cells (800 μg/g). Uptake of a compound by live biomass is principally due to
biodegradation, which in turn depends upon the biodegradability of the compound
in question.
Chitin is a natural homopolymer comprising β-(1-4)-linked N-acetyl-D-glucos-
amine. Chitin is the most abundant and renewable natural polymer. It is found in the
exoskeletons of crabs and other arthropods and in the cell walls of some fungi and is
a waste product of the crab meat canning industry. Due to the presence of one linear
amino group per glucose ring, chitin can be used as a metal ion adsorbent. Dursun
and Kalayci (2005) studied the adsorption of phenol onto chitin as a function of
initial pH, temperature, and initial phenol concentration. The optimum pH value was
determined to be 1.0 and they also found that adsorption capacity increased as the
temperature increased to 40 C. The experimental data fits the Langmuir and
Freundlich adsorption models.
Aksu et al. (2002) has studied adsorption of phenol onto the Mowital B30H resin
immobilized dried activated sludge as a biosorbent. Freundlich and Langmuir
adsorption models were used to represent the column equilibrium data. It was seen
that the adsorption equilibrium data fitted very well to the Langmuir adsorption
model.
1376 S. Busetty
Soil as Adsorbent
In recent decades, studies of the interaction between soils and organics have been
numerous; however, their conclusions have often been contradictory. This is most
likely due to disparity in the different experimental methods adopted and the
different adsorbent/adsorbate systems investigated. Studies have investigated the
adsorption isotherms of benzene and polychlorinated benzenes on dry Woodburn
soil (Chiou and Shoup 1985). The soil environment is a complex system; when
agricultural pollutants enter into the soil system, the concentration present in the soil
system depends on the retention action of the applied agricultural chemicals. The
potential mobility of dissolved chemicals in soils has been described by several
models. The most commonly used isotherm models such as Freundlich and Lang-
muir are used to study chemical waste distribution or segregating between the soil
matrix and the sorbate. Various studies have investigated soil heterogeneity and
kinetics of adsorption–desorption reactions models (Zhu 2002). The soil matrix
system showed widespread hysteretic behavior causing inconsistencies between
adsorption and desorption isotherms. Hysteresis was more distinct with an improved
adsorption reaction time.
Johnson and Sims (1993) conducted batch equilibrium studies of five 14C-labeled
herbicides, including metolachlor, in selected soils The outcomes showed retention
of metolachlor was best correlated with the organic matter content and cation
exchange capacity of the soil.
Peat has been widely used for the adsorption of heavy metals and dye house
effluent from wastewaters due to its excellent ion exchange properties (Leslie 1974;
Belkevich et al. 1976). McKay et al. (1981) conducted experimental batch studies to
determine the parameters that affected surface mass transfer of Astrazone Blue onto
peat during the initial stages of adsorption. They proposed a three-step model: (i) the
mass transfer of dye from the bulk solution to the surface of the adsorbent;
(ii) external diffusion of the adsorbent; and (iii) intra-particle diffusion. McKay
and Allen (1984) used peat as an adsorbent to remove dyes (such as Acid Blue
25, Basic Blue 69, etc.) from aqueous solutions. They also developed a model based
on external mass transfer irreversible adsorption and internal pore diffusion. Cardoso
et al. (1985) investigated the effectiveness of two peat samples for adsorbing selected
heavy metals from aqueous solutions. It was found that peat had a good uptake
capacity for removal of heavy metals from wastewater as well as from the aqueous
solution. The adsorption capacity of copper(II) uptake by peat was limited to
12.6 mg/g. Allen et al. (1992) has investigated sphagnum peat to adsorb copper,
cadmium, and zinc from aqueous solutions. Boyd et al. (1988), Brigatti et al. (1995),
Gutierrez and Fuents (1996), and Lo et al. (1997) have studied exploiting naturally
available clay minerals such as montmorillonite, kaolinite, and illite for the removal
of Zn2+, Pb2+, and cesium and also pental-chlorophenols from aqueous media.
Viraraghavan and Kapoor (1994) investigated removal of mercury form wastewater
using bentonite and reported that 34% of mercury was removed with an initial
concentration of 1 mg/l. Ghiaci et al. (2004) studied the potential of adsorption to
remove hazardous liquids (such as benzene, toluene, and phenol) by organo-zeolites,
which were prepared from synthetic ZSM-5 and natural zeolites. Tayim and
Al-Yazouri (2005) investigated local soil (from the Emirate of Abu Dhabi in the
United Arab Emirates) efficiency in removing heavy metals (such as Pb, Zn, Fe, Cu,
and Mn) from industrial wastewater. The authors concluded that using locally
available soils in an effective and low-cost technique may encourage polluting
industries to be more environmentally sustainable. The results indicated that mont-
morillonite showed a general higher sorption capacity with respect to kaolinite and
that for both the reference clays, in the concentration range investigated.
Maiti et al. (2007) investigated natural laterite as an adsorbent for uptake of
arsenite [As(III)] from aqueous solution. A speciation study revealed that about 20%
of As(III) is converted to As(V). Therefore, natural laterite seemed to play the role of
a natural oxidant for arsenite and the extra step of pre-oxidation of As(III) is not
required. Instead of natural virgin soils, modified soils (chemically and physically)
were used as adsorbents for removal of pollutants from wastewaters in most of the
research. Boyd et al. (1988) used modified smectite with cetyltrimethylammonium
bromide (CTAB-smectite) to adsorb trichloroethylene and benzene and found that
sorption is affected by partition action. Sameer et al. (2003) examined various types
of activated bentonite for removal of phenol from aqueous media, because of
activation bentonite renewed into cationic surfactant bentonite, exhibits maximum
adsorption of phenol. Juang et al. (2003) used surfactant-modified montmorillonite
(treated with cetyltrimethylammonium bromide) as adsorbent for removing phenol,
m-nitrophenol (m-NP), and o-cresol. Akal (2005) studied the effect of treated
pumice on phenol and 4-chlorophenols. The results show a higher adsorption
capacity than that of treated bentonite and vermiculite.
Agriculture and Industrial Residue/By-Products
Agricultural residue, especially cellulose, exhibits adsorbent qualities to treat water

and wastewater. Agricultural residues are economic and eco-friendly due to their
unique chemical composition, abundant availability, renewable nature, and low cost,
making them a viable option for water and wastewater remediation. Through
chemical and thermal treatment, agricultural residues are converted into activated
carbon and are potential adsorbents (Ahmedna et al. 2000). Using this method one
can solve environmental problems and also reduce the preparation costs.
Carbons Prepared from Residues/Wastes
A comparative study of the sorption of different pollutants from water has been
carried out using novel adsorbents prepared by carbonization and subsequent acti-
vation of straw and used rubber tires as well as conventional activated carbons based
on coal, coconut shells, and wood. Pseudo-equilibrium sorption of sorbate equilib-
rium data fitted Freundlich isotherm well and measured values of k and n indicate
that the sorption of sorbate onto derived active carbons is almost identical to that for
1378 S. Busetty
conventional activated carbons. The sorption kinetics of the straw and rubber tire-
based carbons is likewise identical to conventional carbons based on coal and wood
but appreciably faster than the coconut shell sample selected for comparison (Streat
et al. 1995). Srivastava et al. (1997) attempted the removal of pollutants by carbo-
naceous adsorbents obtained from fertilizer waste using 2,4-DNP as the adsorbate
and reported a constant adsorption for the pH range of 2.0–4.0 and a reducing
adsorption trend with a pH more than 4.0, as supported by the pKa value of the
adsorbate (i.e., 3.96), indicating the probable preference of the nondissociated
species of the adsorbate for the negatively charged surface of the carbonaceous
adsorbent. Rengaraj et al. (2000) also examined the suitability of palm seed coat for
the adsorption of ortho-cresol (ocresol) and found it to have an adsorption capacity
of 19.58 mg/g with film diffusion as the rate-limiting step. Tseng et al. (2003)
prepared pine wood-activated carbons at different activation times (0.5, 1.5, 2.7,
and 4.0 h) in steam at 900 C and batch studies were conducted to determine the
adsorption capacity and rate of reaction on to three dyes and three phenols (phenol,
3-chlorophenol, and o-cresol) from aqueous media. For all six adsorbates, the
carbons prepared with a longer activation time had a larger adsorption capacity.
Eucalyptus grandis sawdust, a major waste from the wood industry, was used to
prepare granular activated carbon (GAC) by mixing Powdered activated carbon
(PAC), carboxymethyl cellulose (CMC) as a binder, and kaolin as reinforcer
(Tancredi et al. 2004). In another study, beet pulp, an agricultural low-cost
by-product in the sugar industry, was used to study adsorption phenol by preparing
activated carbon. The BET surface area of the beet pulp carbon was measured as
47.5 mg/g and the maximum adsorption uptake was found to be 89.5 mg/g at the
temperature of 60 C at pH = 6.0. The Langmuir and Freundlich isotherm were used
to fit the experimental data and equilibrium data were well-described by Freundlich
isotherm (Dursun and Kalayci 2005).
Industrial Solid Waste (By-Products/Waste Materials)
Industrial solid wastes (by-products and waste materials) are cheap and locally
available waste materials. The disposal problem relating to these materials is solved
if they are recycled as adsorbents for removing pollutants from the water and waste
waters. Industrial solid wastes such as blast furnace flue dust, slag (generated in
chrome alloy plants), fly ash, and red mud can be used as adsorbents for the removal
of pollutants from the water and waste waters. Singh et al. (1994) studied adsorption
of phenol at different pH values, using fly ash as an adsorbent. The results reveal that
the adsorption capacity of phenol was nearly the same at different pH values.
However, the decreases in pH result in a reduction of the negative charges at the
surface of fly ash, thus enhancing the adsorption of the negatively charged phenolic
ions. In general, the adsorption capacity of phenolic compounds from water and
waste water increases with decreasing pH. The adsorption capacity of phenol
increases with increasing particle size of the sorbate and decreases with increasing
concentration of the sorbate and at lower temperature.
Das and Patnaik (2005) studied phenol removal using industrial waste in the form
of flue dust (from a steel plant) and slag (chrome alloy plants) as adsorbents, with a
removal efficiency of phenol of 90% and 75%, respectively, for these two adsor-
bents. The adsorption process is thermodynamically favorable, spontaneous, and
endothermic in nature. The experimental data are best fitted to the Langmuir
isotherm model. The adsorption of phenol on carbon-rich bagasse flyash (BFA)
was studied by Srivastava et al. (2006). BFA is a solid waste obtained from the
particulate collection equipment attached to the flue gas line of the bagasse-fired
boilers in cane sugar mills. A pH ~ 6.5, adsorbent dose ~ 10 g/l of solution, and
equilibrium time ~ 5 h were found to be optimum conditions for phenol removal
from the solution. The phenol adsorption equilibrium data were fitted to different
isotherm models – Freundlich, Langmuir, Temkin, Redlich–Peterson,
Radke–Prausnitz, and Toth models – using a non-linear regression technique.
Among these isotherms, the Redlich–Peterson isotherm was found to best represent
the data. The change in entropy (ΔS0) and heat of adsorption (ΔH0) for phenol
adsorption on BFA were noted to be 1.8 MJ/kg K and 0.5 MJ/kg, respectively.
Adsorption of phenol on to BFA was spontaneous because of the high negative value
of change in Gibbs free energy (ΔG0).
Agro-Residue as Adsorbent
There have been extensive studies on use of agro-residue as adsorbent. Nawar and
Doma (1989) studied the adsorptive capacities of rice hulls for two industrial textile
dyes and found encouraging results as well successfully applying the Freundlich
model. Kenaf (lignocellulosic fibers) was found to be effective for adsorption of
several toxic heavy metals (namely nickel, copper, zinc, and cadmium) from storm
water. The adsorption potential of these Kenaf plants was found to be related to their
sugar content, extractives composition, lignin content, and physical properties. It
was also found that a decrease in the lignin and cellulose content in Kenaf contrib-
uted to a lower density and easy accessibility of ions to the reactive sites on Kenaf’s
surface, thus increasing the adsorptive capacity (Han 1999). Brown et al. (2000)
demonstrated the relatively lower capacity of raw peanut hulls (and peanut hull
pellets) than that of the ion-exchange resin; yet the substantially lower cost of
production of the former than the latter would probably compensate for their
deficiency more than adequately to justify their use in the treatment of
low-strength metals-contaminated waste streams. Figueiredo et al. (2000) explored
some natural adsorbents comprising chitin, namely squid (Loligo vulgaris) and sepia
(Sepia officinalis) pens and Anodonta (Anodonta cygnea) shells, which were used to
remove color from textile wastewaters and exhibited promising adsorption capaci-
ties. In addition, removal of Cr(VI) from aqueous media was batch studied using the
husk of the Bengal gram (Cicer arietinum). At low concentrations (i.e., 10 mg/l) of
chromium the removal efficiency was found to be 99.9% (Ahalya et al. 2005). The
adsorption capacity of castor seed shell (CSS), a solid waste agricultural by-product,
was used to remove methylene blue from wastewater; the adsorption capacity was
1380 S. Busetty
found to be 158 mg/g (Oladoja et al. 2008). Xue et al. (2008) studied removal of two
basic dyes, namely malachite green and methylene blue, which were removed using
rice bran and wheat bran by-products as adsorbents. Recently, there has been
increasing interest in evaluating the use of practically every possible natural adsor-
bent for adsorption, resulting in various degrees of success.
Besides naturally available soils and agro-residue (biomass), the use of several
chemically synthetic and non-biodegradable wastes as adsorbents has been
attempted by several researchers. Although non-biodegradable wastes are naturally
of lower adsorption capacity than the naturally available soils and agro-reside-based
adsorbents, due to their increased magnitude and resultant solid-waste disposal
problems, attempts have been made to find at least some use for them, including
in the field of adsorption. Luchesi and Maschio (1983) used carbon (with a surface
area of 320 m2/g), produced from stripped-tire rubber, as an adsorbent for removal of
Orange II and Acid Black 24 dyes from the aqueous phase. The Freundlich isotherm
adsorption model was used to express the sorption phenomenon of the sorbate.
Rengaraj et al. (2002) further investigated activated carbon prepared from rubber
seed coat (RSCC), an agricultural waste by-product, for removing phenols from
aqueous solution. They found that RSCC is 2.25 times more efficient than Com-
mercial Activated Carbon (CAC). Tanthapanichakoon et al. (2005) investigated the
liquid-phase adsorption–desorption characteristics of reactive dyes. The ethanol regen-
eration efficiency of the prepared AC saturated with either tested dye was found to be
higher than that of the commercial Activated Carbon (AC).
Correlation and Estimation of Performance of Adsorption

Systems
A variety of different isotherm equations have been proposed, some of which have a
theoretical foundation and some being of a more empirical nature. Many of these
equations are valid over small relative pressure ranges but do not fit the experimental
data when tested over the full range of relative pressures. Only those that are
generally used for the surface of porous adsorbents are outlined here. Large numbers
of researchers in the field of environmental engineering have used Freundlich and
Langmuir isotherm equations to represent equilibrium adsorption data using acti-
vated carbon–organic contaminants systems. To determine the adsorption potential
of the soil and soil agro-based adsorbents for the removal of phenol, study of
adsorption isotherms has been carried out and tested against multi-parameter iso-
therm models (up to five parameters): two-parameter models – Langmuir,
Freundlich, Modified Langmuir–1, Modified Langmuir–2, Dubinin–Radushkevich,
and Temkin; three-parameter models – Langmuir–Freundlich, Redlich–Peterson,
Sip, Fritz–Schlunder model, Radke–Prausnitz model, Toth model, and Jossens
model; four-parameter models – Fritz–Schlunder model, and Baudu; and five-
parameter model – Fritz–Schlunder.
In an adsorption study, describing the sorption process and evaluation of the best-
fitting isotherm model is a key analysis to explore the theoretical hypothesis.
Hence, several statistical analyses have been widely used to estimate the validity of
the experimental equilibrium adsorption values with the predicted equilibrium
values. Several error analyses have been carried out (average relative error deviation
[ARED], Marquardt’s percentage standard error deviation [MPSED], hybrid frac-
tional error function [HYBRID], sum of the squares of the errors [SSE], correlation
coefficient, and residuals).
All of these isotherm models are derived based on theoretical assumption, and
several error deviation functions have been used to adequately measure the goodness
of fit of the models, such as the correlation coefficient (r2), SSE, ARED, MPSED,
HYBRID, and residual analysis (RESID). However, the very approach of lineariza-
tion of the non-linear models necessarily yields rationalization of specific variables,
which may have significant bearing on the adsorption process itself.
The generalized isotherm studies are being carried out to identify the suitability
of selected raw/treated adsorbents. The study of adsorption of the pollutants at
equilibrium concentration (at constant temperature) is referred to as adsorption
isotherm.
Isotherm Modeling
Bi-Parameter Model
Langmuir Isotherm Model

The two-parameter Langmuir’s isotherm equation is as follows:
x q bC e
qe ¼ ¼ m (2)
m 1 þ bC e
where x is the amount of adsorbate adsorbed (mg), m is the mass of adsorbent (g),
Ce is the equilibrium concentration of the solute in the bulk solution (mg/l), qe is the
amount of solute adsorbed per unit weight of adsorbent at equilibrium (mg/g), qm is
the maximum adsorption capacity (mg/g), and b is the constant related to the free
energy of adsorption (l/mg). The Langmuir model is generally a better model for the
adsorption of gases onto solids, whereas the Freundlich model is a better model for
the adsorption of liquid solutions (Cooney 1999). The simplified form of the
Langmuir equation is given as follows:
Ce Ce 1
¼ þ (3)
qe qm bC e
Freundlich Isotherm Model

The Freundlich model is by far the most widely used isotherm model to determine
maximum adsorption capacity (Cooney 1999). The two-parameter Freundlich model
is as follows:
1382 S. Busetty
x
¼ qe ¼ k f C 1=n
e (4)
m
where x is the mass of solute adsorbed (mg), m is the mass of adsorbent (g), Ce is the
final aqueous phase concentration (mg/l), kf and n are empirical constants, and qe is
the amount of adsorbate adsorbed per unit mass of adsorbent. The value for the
constant kf is typically reported at a water-phase equilibrium concentration of 1 mg/l
(i.e., Ce = 1), when the equation is transformed to the form mx ¼ k f , and, thus,
k (adsorptive capacity) has the units of w/w or mg/g for the example stated. The
Freundlich model assumes that the energy distribution for the adsorption sites is
exponential in nature (Cooney 1999). At high concentrations, the equation would
fail to fit experimentally (Cooney 1999). In such cases, the logarithmic form of the
Freundlich equation can be expressed as follows:
x 1
log ¼ log qe ¼ log k f þ log C e (5)
m n
The linear line obtained gives a slope, which is the value of 1/n, and the
Y-intercept is log k. The lower the slope, the better the adsorption, over the entire
range of concentrations, whereas the steeper the slope, the better the adsorption at
high concentrations. A greater value of ‘kf ’ indicates a higher capacity of adsorption.
Modified Langmuir–1
The modified Langmuir–1 is given as follows:
bT n C e
qe ¼ (6)
1 þ bC e
where qe is the amount of adsorbate adsorbed per unit mass of adsorbent, Ce is the
final aqueous phase concentration (mg/l), T is the temperature (in Kelvin), and b is
the constant related to the free energy of adsorption (expressed as l/mg).
Modified Langmuir–2
The modified Langmuir–2 is given as follows:
!
bC e 1 þ σ 2 ð1 bC e Þ
qe ¼ (7)
1 þ bC e 2ð1 þ bC e Þ2
where qe is the amount of adsorbate adsorbed per unit mass of adsorbent, Ce is the
final aqueous phase concentration (mg/l), and σ is the isotherm constant related to the
degree of sorption.
Dubinin–Radushkevich Isotherm
Dubinin–Radushkevich isotherm is often used to estimate the characteristic porosity
in addition to the apparent free energy of adsorption. Thus, for evaluating these
parameters the Dubinin–Radushkevich isotherm is used in the following form:
" 2 #
1
qe ¼ K DR exp b RTln 1 þ (8)
Ce
where qe is the equilibrium adsorption capacity (mg/g), Ce is the adsorbed equilib-

rium concentration (mg/l), KDR relates to the free energy of sorption, and b is the
Dubinin–Radushkevich isotherm constant related to the degree of sorption.
Temkin Model
The Temkin isotherm is typically expressed in the following form:
RT
Qe ¼ ðlnAC e Þ (9)
b
where Qe is adsorption equilibrium capacity (mg/g), Ce is the adsorbed equilibrium
concentration (mg/l), and A and b are the isotherm constants.
Three-Parameter Models
Langmuir–Freundlich Isotherm
The Langmuir–Freundlich isotherm is given as follows:
qmLF ðK LF C e ÞmLF
qe ¼ (10)
1 þ ðK LF C e ÞmLF
where qe is the adsorbed amount at equilibrium (mg/g), qmLF is the Langmuir–Freundlich

maximum adsorption capacity (mg/g), Ce is the adsorbed equilibrium concentration
(mg/L), KLF is the equilibrium constant for a heterogeneous solid, and mLF is the
Langmuir–Freundlich heterogeneity parameter which lies between 0 and 1. The
Langmuir–Freundlich isotherm model at low sorbate concentrations effectively
gets reduced to the Freundlich isotherm and thus does not follow Henry’s law.
At high sorbate concentrations, it behaves as monolayer sorption and shows the
Langmuir isotherm characteristics.
Fritz–Schlunder Equation
The Fritz–Schlunder model equation is given as follows:
qmFS K FS C e
qe ¼ (11)
1 þ qmFS C e /
where qe is the adsorption equilibrium capacity (mg/g), Ce is the equilibrium

concentration of the adsorbate (mg/L), qmFS is the Fritz–Schlunder maximum
adsorption capacity (mg/g), KFS is the Fritz–Schlunder equilibrium constant
(L/mg), and α is the Fritz–Schlunder model exponent.
1384 S. Busetty
Radke–Prausnitz Models
The Radke–Prausnitz model equation is given as follows (Vijayaraghavan et al. 2006):
qmRP K RP C e
qe ¼ (12)
ð1 þ K RP C e ÞmRP
where qe is the equilibrium adsorption capacity (mg/g), qmRP re the Radke–Prausnitz

maximum adsorption capacities (mg/g), Ce is the adsorbate equilibrium concentra-
tion (mg/l), KRP are the Radke–Prausnitz equilibrium constants, and mRP are the
Radke–Prausnitz model exponents.
Toth Model
To reduce the error between experimental and theoretical values, Toth has modified
the existing Langmuir isotherm. The Toth model equation is given as follows:
C e qmT
qe ¼ mT1 (13)
1
KT þ C mT
e
where qe is the adsorbed amount at equilibrium (mg g1), Ce is the equilibrium

concentration of the adsorbate (mg l1), qmT is the Toth maximum adsorption capacity
(mg g1), KT is the Toth equilibrium constant, and mT is the Toth model exponent.
Jossens Model
The Jossens model is as follows:
qe
Ce ¼ exp Fqpe (14)
H
where qe is the adsorbed amount at equilibrium (mg/g), Ce is the equilibrium concen-
tration of the adsorbate (mg/L), and H, F, and p are Jossens constants. H and F depend
only on temperature. This equation can reduce to Henry’s law at low capacities.
Redlich–Peterson Model
The Redlich–Peterson (1959) model is a three-parameter model given by:
x AC e
qe ¼ ¼ (15)
m 1 þ BC βe
The linearized form is:

AC e
ln 1 ¼ lnB þ β lnC e (16)
qe
where x is the moles of adsorbate adsorbed (mg), m is the mass of the adsorbent (g),
and Ce is the final adsorbate concentration (mg/l).
The three constants are A, B, and β. The parameter A is measured in units of mg/g, B is
h units ofi (l/g), and β lies between 0 and 1 (Redlich and Peterson 1959).
measured in the
Plotting ln ACq 1 against lnCe yields a straight line of slope β and intercept
e
e
lnB. However, plotting of this equation is not applicable because of the three
unknown parameters contained within the equation. Therefore, a minimization
procedure is adopted (for maximum R2 correlation coefficient) between the theoret-
ical data for qe predicted from Eq. 15 and the experimental data.
RT RT
qe ¼ lnðK T Þ þ ln ðC e Þ (17)
bT bT
where 1/bT indicates the adsorption potential of the adsorbent and KT is the Temkin
isotherm constant. Temkin isotherm contains a factor that explicitly takes into
account the interactions between adsorbing species and the adsorbate. This isotherm
assumes that (i) the heat of adsorption of all the molecules in the layer decreases
linearly; and (ii) adsorption is characterized by a uniform distribution of binding
energies, up to a maximum binding energy (Kim et al. 1997).
Sip Model
The Sip isotherm model equation is expressed as follows:
ðK S C e Þβ
qe ¼ h i (18)
1 þ ðαS C e Þβ
where KS (l/g) and α (l/mg)β are the Sip isotherm constants and β is the exponent that
lies between 1 and 0.
Four-Parameter Models
Fritz–Schlunder Model
The Fritz–Schlunder isotherm model equation is expressed as follows:
AC /
qe ¼ e
(19)
1 þ BC βe
where A and B are the Fritz–Schlunder parameters and α and β are the
Fritz–Schlunder equation exponents.
Baudu
The Baudu equation is expressed as follows:
qm b0 C ðe1þxþyÞ
qe ¼ (20)
1 þ b0 C ðe1þxÞ
1386 S. Busetty
where qm is the Baudu maximum adsorption capacity (mg/g), b0 is the equilibrium

constant, and x and y are the Baudu parameters.
Five-Parameter Model
Fritz–Schlunder Model
The Fritz–Schlunder model equation is expressed as follows:
qmFSS K 1 C m 1
qe ¼ e
(21)
1 þ K 2Ce m2
where qmFSS is the Fritz–Schlunder maximum adsorption capacity (mg/g) and K1,
K2, m1, and m2 are the Fritz–Schlunder parameters.
Estimation of Best-Fitting Isotherm Model
Error Functions
ARED is used to minimize the fractional error distribution across the entire concen-
tration range:

1 X Qe,cal Qe,exp
ARED ¼ 100 (22)
N Qe,exp
The SSE, the most widely used error function, has a major drawback. The
theoretical isotherm parameters calculated from the sum of the squares of the error
function will result in a better fit at the higher end of the sorbate concentration range.
This is due the magnitude of the errors, and hence the error function will increase as
the concentration increases.
X 2
SSE ¼ Qe,cal Qe,exp (23)
HYBRID is an error function that was developed to improve the SSE at low
concentration values. In this task, each sum of the squares of the error values was
divided by the theoretical adsorbent-phase concentration value.

1 X Qe,exp Qe,cal
HYBRID ¼ 100 (24)
N P Qe,exp
The MPSED is an error function distribution that follows the geo-

metric mean error, which allows for the number of degrees of freedom of the
system.
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uP 2
u ðQexp Qcal Þ =
t Qexp
MPSED ¼ 100 (25)
N P
The sum of the absolute errors (EABS) is similar to the SSE function and
provides a better fit at higher concentrations for the isotherm parameters:
p
X

EABS ¼ Qe,exp Qe,cal (26)
i¼1
Statistical Functions
Pearson’s correlation coefficient (r) is a sampling index that shows the degree
linearity between two dependent data series. The degree of linearity varies from
1 to 1.
P P P
N ð XY Þ ð X Þð Y Þ
r ¼ rhffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiiffi h i (27)
P P P P
N X 2 ð X Þ2 N Y 2 ð Y Þ2
The coefficient of determination (r2) explains the regression line with the per-
centage of variability in the dependent data series variable. The percentage degree
varies from 0 to 1.
S2
r2 ¼ (28)
S ðXY Þ S ðYY Þ
where SXY is the sum of squares of X and Y, and SYY is the sum of squares of Y. In
addition to above mentioned error and statistical functions, the Chi-square test was also
examined to predict the best-fitting isotherm models.
Kinetic Study
Adsorption Kinetics
Adsorption kinetics are the most important to evaluate and analyze process effi-
ciency. Hence, the equilibrium time and adsorption capacity plays a major role in the
design. Sorption equilibrium is recognized once the concentration of sorbate in the
bulk solution is in dynamic stability with that of the boundary. The steady analysis is
the most vital evidence required to evaluate the affinity. It is consequently important
to define in what way the rate of reaction depends on the concentrations of sorbate
1388 S. Busetty
and also how adsorbent characteristics affect the rate of reaction. From the kinetic
analysis, the equilibrium time can be determined, which in turn indicates adsorption
process completion. Various kinetic models have been used by researchers, using the
pseudo-first-order (Vasanth et al. 2007; Ho and McKay 1999) and pseudo-second-
order models (Ho et al. 2000).
Pseudo-First-Order Kinetics
The interaction between adsorbate and adsorbent can be explained by

reversible equilibrium kinetics (Fogler 1998). The Lagergren rate equation is the
most widely used kinetic first-order equation (Tseng et al. 2003; Ho and McKay
2004):
dqt
¼ k t ð qe q t Þ (29)
dt
where kt (l/min) is the pseudo-first-order rate constant, and qe and qt are the sorption
capacity at equilibrium and time t (mg/g). After integration by applying the condi-
tions qt = 0 at t = 0 and at t = t, qt = qt, Eq. 31 becomes:
kt
logðqe qt Þ ¼ logqe t (30)
2:303
The value of kt can be calculated from the plots of log(qe qt) versus t for
different concentrations of phenol.
Pseudo-Second-Order Kinetics
The pseudo-second-order chemisorption kinetic rate equation (McKay and Ho 1999)

is expressed as follows:
dqt
¼ k 2 ðqe qt Þ2 (31)
dt
where k2 is the second-order rate constant (g/mg min). After integration by appalling
the conditions qt = 0 at t = 0 and at t = t, qt = qt, Eq. 31 becomes:
t 1 t
¼ 2
þ (32)
qt k 2 qe qe
Equation 32 can be written as follows:
t 1 t
¼ þ (33)
qt h qe
where h = k 2 q2e , by plotting of qt versus t has a linear relationship. The values of k2

t
and qe can be calculated from the intercept and slope of the plots of qt versus t.
t
Elovich Equation
The Elovich equation is a useful model; it can be expressed as follows (Aharoni and
Tompkins 1970):
dqt
¼ αexpðβqt Þ (34)
dt
where α is the initial adsorption rate (mg g1 min1) and β is the desorption constant
(g mg1) during any one experiment.
To simply the Elovich equation (34) assume αβt >> t, and by applying boundary
conditions qt = 0 at t = 0 and qt = qt at t = t, Eq. 34 becomes:
1 1
qt ¼ lnðαβÞ þ lnðt Þ (35)
β β
The plot between qt versus ln(t) yields a linear relationship with a slope of β1 and
an intercept of β1 lnðαβÞ . The term β1 indicates the number of sites available for
adsorption.
Thermodynamic Studies
Study of adsorption involves mass transfer operations, chemical reactions, and

energy variations. During these operations, thermodynamic principles are involved.
To study the spontaneous nature of adsorption, the thermodynamic parameters
should be essentially determined.
Fundamentals of Thermodynamics
This section explains the changes in the physical and chemical energy that takes
during the thermodynamics effect. Thermodynamics can be roughly encapsulated
with the following three parameters: enthalpy (ΔH0), entropy (ΔS0), and free energy
(ΔG0) (Mehrian et al. 1991). The work done by the system can be explained by
change (endothermic or exothermic) in the enthalpy of a system, which is equal to its
heat output at a constant pressure. A negative value of ΔH0 represents energy
coming out of the system and indicates the process as exothermic and the sorption
behavior as physio-sorptive in nature. It also indicates the free diffusion of molecules
through bulk solution. The positive value of ΔH0 indicates the process as
1390 S. Busetty
endothermic and the sorption behavior as being due to chemical bonding or chem-
isorption (Piatt et al. 1996).
Entropy (ΔS0) is a measure of the disorderliness of a system. With the increase in
entropy significance a spontaneous change occurs in a system. The positive values of
ΔS0 show the increased uncertainty at the solid/solution boundary during the adsorp-
tion process. An extemporaneous reaction is one that happens deprived of any outside
interference. The negative value of ΔS0 is due to loss of freedom as the molecules
adsorb to the surface. The reversibility of the system was explained by a value of ΔS0
less than 1 (Brucher and Bergstrom 1997; Catena and Bright 1989). Developments that
are impulsive in one course are non-spontaneous in the reverse direction.
The free energy (ΔG0) of the system is defined as the work done by the system at a
constant temperature and pressure. Negative values of ΔG0 would anticipate a favorable
response and specifies the impulsive nature of the adsorption process. The increasing
values of ΔG0 with an increase in temperature show that the impulsive nature of
adsorption is inversely proportional to temperature (McCloskey and Bayer 1987).
Column Study
Fixed-Bed Adsorption Column
Adsorption of pollutants from industrial wastewaters or gaseous pollutants can be

achieved by allowing fluid flowing through the fixed granular bed. To evaluate the
feasibility and economics of the adsorbent, a laboratory study is usually conducted.
The batch study gives the removal capacity of specific waste contaminants, but the
continuous flow provides a practical application of the process. For industrial
applications, a fixed-bed adsorption column study is an important step. In order to
stop the adsorption period in a process before saturation, a thorough understanding
of adsorption characteristics is necessary (Bautista et al. 2003). The column study for
adsorption starts with prototype testing to create the breakthrough curve. The
amount of adsorbate adsorbed within a bed depends both on space and time. The
sorbate passes into the bed, and it immediately contacts the first few strata of
absorbent. As the top strata of adsorbent become saturated with adsorbate, the
mass transfer zone (MTZ) will move down in the bed until breakthrough occurs.
The depth of the MTZ depends on the hydraulic loading rate and the characteristics
of the adsorbent. The point at which the outlet concentration of the fluid starts to rise
is known as the “breakpoint” and the point at which the effluent concentration almost
equals the influent concentration is known as the “exhaust point.” For a narrow
MTZ, the breakthrough curve is very steep. If the mass transfer rate is faster and no
axial dispersion is present, then the MTZ width would be zero and the breakthrough
curve would be a vertical line. The overall dynamics of the system determine the
efficiency of the system.
Adsorption ability is calculated by plotting a graph of concentrations versus time.
By integrating the following equation, adsorption capacity can be measured in terms
of time units:
ð
1
C
tt ¼ 1 dt (36)
co
0
where tt is the time to total capacity. In operation, the process needs to be stopped to
get the “usable” capacity and the curve can be integrated as follows:
ð
t break
c
t Usable ¼ 1 dt (37)
co
0
Further, most of the time the breakthrough time is very close to the time elapsed at
usable capacity. The capacity times are directly related to bed depth:

t usable
H Used ¼ H Total (38)
t Total
Therefore:

t usable
H unused ¼ 1 H Total (39)
t Total
HUnused represents the MTZ. It depends on the fluid velocity and is independent of
the total length of the column. HUsed is directly proportional to tbreak. The unused
depth can also be readily measured in experiments. The total design depth of a bed is
determined by adding the required usable capacity to the unused height:
H Total ¼ H Used þ H unused (40)
Bed Depth Service Time (BDST)
In a column study a continuous mass transfer can be determined between two phases,
i.e., the sorbate and the adsorbent as a fixed bed. It is a function of the depth of the
zone and contact time. The aim of the column study is to study the effect of several
experimental trails on the bed depth service time (BDST) model. The BDST model
describes a correlation between the service time of the column and the fixed-bed
column. The original work on the BDST model was carried out by Bohart and
Adams (1920). The BDST equation is as follows:
h i
ln Co
=Ce 1 ¼ ln eKN 0 H=V 1 K C o t (41)
where Co is the influent concentration (mg/l), Ce is the allowable effluent concen-

tration (mg/l), K is the rate constant [m3/kg of adsorbent (h)], No is the adsorptive
1392 S. Busetty
capacity (kg of contaminant/m3 of adsorbent), H is the depth of adsorbent bed (m),

V is the linear flow rate (m/h), and t is the time in hours.
Since eKN 0 H=V >> 1, Eq. 41 can be rewritten as:

No V Co
t¼ H ln 1 (42)
CoV KN o Ce

No H 1 Co
t¼ ln 1 (43)
C o V KN o Ce

No 1 Co
t¼ ½H ln 1 (44)
CoV KC o Ce
Biodegradation
Bioremediation is a low-cost technology for attacking sites polluted with organic

pollutants (Yeom and Ghosh 1998). The governing and methodological challenge is
to use low-cost technologies that can Identify complex organic mixtures in polluted
soils and thus reduce the threat to human health and the environment. The challenge
is also to decrease the toxicity of the organics and the movement of potential
hazardous elements being treated. Thus, bioremediation is a long-term risk-protec-
tive process because it acts as a source elimination, pollution-lowering, and risk-
lowering technique to prevent ground water contamination and therefore decreases
the necessity for additional expenses.
Although several bioremediation procedures are in use, selecting the process
suitable for a specific site is a function of the remediation objectives to be attained,
the physical and chemical characteristics of the substrate to be treated, the environ-
mental circumstances that are formed, the materials handling and equipment neces-
sary, and the availability of funds.
Several studies have been conducted in the past to test aerobic degradation
of phenol. Most of the laboratory studies reported had involved pure strains of
microorganisms isolated from naturally occurring systems (Erik et al. 1989). Accli-
mation of the microorganisms to the organic compound in question has been an
important step in the biodegradation process. It could also differ depending on
concentration, environment, temperature, aeration status, and other often undefined
factors (Alexander 1994). Buitron et al. (1993) have used organisms obtained from
activated sludge to degrade 50 ppm of phenol in less than 2 h. D’Aquino et al. (1988)
performed experiments to try and degrade high concentrations of phenol as seen in
industrial effluents within a 24 h period. They successfully isolated two strains of
bacteria (Pseudomonas and Acinetobacter). Both strains were able to completely
biodegrade phenol and benzoate at concentrations above 200 ppm within 12–16 h.
A heterogenous mixture of microbial population from swine waste was tested for
its ability to degrade phenol. This consortium readily oxidized phenol and p-cresol
under aerobic conditions (Ishaque et al. 1985). Biodegradation of phenol using

yeast and fungi has been studied by Katayama et al. (1991), Kennes and Lema
(1994), and Anselmo and Novais (1992). Most of the fungi degrade xenobiotics by
co-metabolic reactions, only a few being able to utilize phenol as their sole source
of carbon and energy. Cordova-Rosa et al. (2009) have studied remediation of
phenol-contaminated soil by a mixed bacterial culture and isolated Acinetobacter
calcoaceticus obtained from a coal wastewater treatment plant containing high
phenolic compounds.
Cross-References

▶ Decentralized Integrated Approach of Water and Wastewater Management in
Rural West Bengal
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2498
Making Artificial Beachrock Through
Bio-cementation: A Novel Technology 57
to Inhibition of Coastal Erosion
Md. Nakibul Hasan Khan and Satoru Kawasaki
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1400
Beachrock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1402
World Distribution of Beachrock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1402
Properties of Beachrock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1404
Age of Beachrock Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1404
Origin of Beachrock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1407
Artificial Beachrock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1408
Formation of Artificial Beachrock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1408
Bio-cementation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1409
Bio-cementation Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1409
Microbially Induced Carbonate Precipitation (MICP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1412
The Role of Urease Activity in Carbonate Precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1412
Cementation Process Through Bacterial Action . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1413
Applications of Carbonate Precipitation Through Bacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1415
Sand Cementation Through Bacterial Carbonate Precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1417
Inhibition of Coastal Erosion Through Artificial Beachrock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1418
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1419
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1420
Abstract
Coastal erosion is a significant problem throughout the world. In order to prevent
or minimize damage from erosion, combinations of various structures have been
used traditionally. The maintenance and management for repairing and rebuilding
the coast are expensive. As a hint for an alternative material in order to reduce
M. N. H. Khan (*)
Department of Environmental Science and Engineering, Jatiya Kabi Kazi Nazrul Islam University,
Mymensingh, Bangladesh
S. Kawasaki
Faculty of Engineering, Hokkaido University, Sapporo, Japan

https://doi.org/10.1007/978-3-319-73645-7_38
1400 M. N. H. Khan and S. Kawasaki
life-cycle costs, it is focused on the beachrock. A beachrock is composed of

coastal sediments that have been cemented mainly by CaCO3 within the intertidal
zone, and its formation period is much shorter than that of other sedimentary
rocks. The cement component of beachrocks mainly consists of either calcium
carbonate or silica. Compared to the concrete structure, coral sand solidification
would be considered to minimize cost. A variety of factors in the formation of
beachrock has been considered. Among them are the possibility of solidification
promotion by microbial action, the urea decomposition action of microorganisms,
and the microbially induced carbonate precipitation (MICP) method; as princi-
ples, carbon dioxide generates as well as precipitates CaCO3 by microbial
metabolism. Bio-cementation technology is used to make artificial beachrock.
Bio-cementation is a sand solidification technology, in which ureolytic bacteria
release carbonate from urea hydrolysis in the presence of an excess of calcium
ions to form calcite (CaCO3). Bio-cementation is to enhance the strength and
stiffness properties of soil and rocks through microbial activity or products.
Bacterial CaCO3 precipitation under appropriate conditions is a general phenom-
enon where the ureolytic bacteria uses urea as an energy source and produces
ammonia which increases the pH in the environment and generates carbonate,
causing Ca2+ and CO32 to be precipitated as CaCO3. This CaCO3 joins sand
particles and forms rocklike materials that auto-repairs by means of sunlight,
seawater, and bacteria as microbially induced carbonate precipitation method.
These rock particles produced artificially are called artificial rock, and this
artificial rock has the potentiality to protect coastlines from erosion.
Keywords
Beachrock · Artificial beachrock · Bio-cementation · Coastal erosion · Calcite
precipitation · Ureolytic bacteria · Urease · Sand cementation · Microbially
induced · Carbonate precipitation · Erosion · Coastal sediment · Calcium
carbonate · Cement · Microorganism
Introduction
Some islands in the world are in danger of being submerged due to erosion and sea
level rise as impacts of climate change. Erosion of the sandy shore is often used to
refer to changes in the coastline due to the collapse of the sediment balance. Coastal
erosion has been a significant problem globally due to anthropogenic changes along
the coastline. In order to prevent, or at least minimize damage from erosion, a
combination of various structures and processes has been traditionally used, includ-
ing embankments, revetments, jetties, artificial reefs, offshore breakwaters, and sand
bypassing (Danjo et al. 2014). But installment and management of these technolo-
gies are expensive.
The use of inexpensive alternative materials should be considered, to cope
with the increase in costs related to the maintenance and management of concrete
structures. In this regard, Danjo and Kawasaki (2013a) focused on alternative
57 Making Artificial Beachrock Through Bio-cementation: A Novel. . . 1401
materials to replace beachrock to reduce life-cycle costs associated with the

currently employed methods. Beachrock forms much more quickly than other
sedimentary rocks within the intertidal zone and is composed of coastal
sediments that have been cemented together mainly by CaCO3 (Danjo and Kawa-
saki 2013a). By using the processes that solidify beach sand, we hypothesized
that we could create a highly durable artificial beachrock that would be
comparable in efficacy to the existing concrete structures. Artificial beachrocks
(manufacture artificially in the natural condition) have the potential to inhibit
coastal erosion (Danjo et al. 2013b). Beachrocks are coastal deposits cemented
mainly by calcium carbonate cement; these deposits are found in the tidal and
intertidal zone of sandy beaches in tropical and subtropical regions (Danjo and
Kawasaki 2013a).
For the formation of beachrock, various factors have been considered. Among
them, Danjo and Kawasaki (2014), focused on the possibility of promoting solidi-
fication by microbial processes, specifically urea decomposition by microorganisms.
In this study, the microbial induced calcium carbonate precipitation (MICP) method
was utilized, which relies on the microbial metabolism of urea that generates carbon
dioxide and precipitates CaCO3 (Whiffin et al. 2007). This low environmental
impact method was assessed to determine its efficiency as an alternative means to
alleviate coastal erosion. Considering the use of artificial rock in order to preserve
such submerged-looking islands above sea level, Danjo and Kawasaki (2012) and
Danjo et al. (2012) conducted several studies in Okinawa and Ishikawa, Japan. They
found sufficient information to build artificial beachrock.
Bio-cementation is to enhance the strength and stiffness properties of soil and
rocks through microbial activity or products. It could be used to prevent soil
avalanching, reduce the swelling potential of clayey soil, mitigate the liquefaction
potential of sand, and compact soil on reclaimed land sites (Ivanov and Chu 2008).
Traditional grouting methods for ground improvement employ particulate (cement/
bentonite) or chemical grouts that can be rather expensive and environmentally
unfriendly (Ivanov and Chu 2008). Recently, novel grouting techniques have been
developed to treat unsaturated coarse soils by stimulating natural processes (DeJong
et al. 2006; Whiffin et al. 2007). One of these methods, termed biogrouting, has
shown some promise in soil cementation via microbially induced carbonate precip-
itation (MICP). This approach mimics natural processes by depositing calcite
(CaCO3) on the soil grains, thereby increasing the material’s stiffness/strength and
reducing its erodibility.
In ground treatment applications for sandy soil, the deposition of calcite over the
grain surfaces and around the grain contacts creates a sandstone-like material. In
principle, MICP treatment protocols can be tailored to produce a more targeted
deposition of calcite around the grain contacts, with the porosity decreasing by less
than 10% (Shahrokhi-Shahraki et al. 2015). Hence, significant improvements in the
geomechanical properties can be achieved while maintaining permeability.
In this chapter beachrock, its global distribution, origin, artificial beachrock,
formation of process of artificial beachrock, and its potentiality to protect coastal
erosion are discussed.
Beachrock
Beachrock is a type of sedimentary deposit that generally occurs on tropical and

subtropical beaches as a result of intertidal lithification of loose beach sands and
gravels by carbonate cementation (Ginsburg 1953). The Association for the Geo-
logical Collaboration in Japan (2000) defined beachrock as follows:
An extremely recent, consolidated, calcareous rock occurring in the intertidal zone on sandy
beaches. It comprises multiple layers, each around 1–60 cm thick, and runs roughly in the
same direction as the beach, at an oblique angle of 5–7 to the sea. It forms a cuesta shape,
with the landward side having an acutely angled face. Its overall thickness is about 1.0 m,
and may be separated into two or more bands. The cement material may be calcareous or
may contain iron, and the non-cement substances may be any material, regardless of the
grain size or substance. Beachrocks are found on beaches in tropical and sub-tropical zones.
In the seas around Japan they can be found in the Nansei Island group, which is southwest of
the mainland.
Around the world beachrocks have been reported to form over several thousand
years owing to interactions among sand supply, cement precipitation from seawater,
and coastal erosion by ocean waves (Danjo and Kawasaki 2013a). An example of
beachrock of Okinawa, Japan, is shown in Fig. 1.
World Distribution of Beachrock
The geographic distribution of beachrocks around the world is shown in Fig. 2.

As can be seen in the figure, over 90% of beachrocks are distributed between
the proximity of 40 N and the Tropic of Capricorn. This proportion, however,
does not represent the total size of the distribution area but rather the number of
significant distributions. A large number of beachrocks are located in the Aegean
coast (Area A), southern India (Area B), the Great Barrier Reef (Area C), the West
Indies (Area D), and eastern Brazil (Area E). The northernmost point for the
beachrock distribution was in Scotland (40 57/N), while the southernmost point
was in South Africa (34 60/S).
The geographic distribution of beachrocks was not concentrated near the equator.
In particular, high concentrations of beachrocks were found at relatively high
latitudes such as Area A. This precludes the notion that beachrocks are concentrated
only in areas where the temperature of the air or sea is high. Though, it is difficult to
determine why beachrocks are distributed the way they are. For example, in Area B
beachrocks are distributed in the south and northwest of India but not in the
southwest region. Similarly, there are no beachrock occurrences in the eastern area
of Africa, except in areas close to the equator.
Beachrocks throughout the world are found in a consolidated state in close
proximity to non-consolidated sediments, as is shown in Fig. 1, which shows
Fig. 1 Beachrock in Motobu,

Kunigami, Okinawa, Japan
(Danjo and Kawasaki 2013b)
Fig. 2 Beachrock distribution in the world (Danjo and Kawasaki 2013b)
beachrock in Okinawa, Japan. This suggests that the conditions that led to their
formation are complex (Danjo and Kawasaki 2013b). There may be a tendency for
beachrocks to form in places where the ocean currents are calmer, such as in Area A,
which is surrounded by land, and in Area C, which is surrounded by coral reefs.
However, there is a need for further research to identify why beachrocks form in
some places and not others.
Fig. 3 Beachrock India (Vattakottai) India (Tiruchendru)

compositions around the India (Kanyakumari) Japan (Okinawa)
world (Khan et al. 2015)
Japan (Ishikawa) Bangladesh (Satkhira)
100
90
80
70
60
% 50
40
30
20
10
0
CaO SiO2 Al2O3 TiO2 FeO
Properties of Beachrock
More than 90% of beachrocks are distributed between 40 N latitude and the Tropic
of Capricorn and that their formative periods range from 26,000 years to just a few
decades ago (Danjo et al. 2013a). But there is no relation between the formative age
of beachrock and latitude (Danjo and Kawasaki 2012).
Chemically, beachrock around the world differs in composition (Fig. 3).
Beachrock at Tiruchendur, India, mainly consists of Ca. In contrast, the beachrock
in Vattakottai, India, is mainly rich in Si and Al, and that in Kanyakumari, India, is
mainly rich in Fe and Ti (Danjo and Kawasaki 2012) where Bangladesh is rich in Si
(Fig. 3). The main components of beachrocks and surrounding material are calcium
carbonate or silica (Danjo et al. 2013a). The proportion of CaCO3 in beachrocks was
around 90%, while the other portions consisted of SiO2 and Al2O3 in the Gulf of
Mannar, India (Sahayam et al. 2010). The beachrocks are mainly composed of
calcium carbonate or silica, similar in Japan and the world (Table 1) and (Fig. 4).
Age of Beachrock Formation
The formative periods for beachrocks in the world are shown in Fig. 5. The
periods were determined using four methods: carbon-14 dating, optically stimulated
luminescence (OSL), content analysis, and the relationship between present-day
sea levels and changes in sea level (Danjo and Kawasaki 2013b). The units used
to describe the periods were yrBP or yBP for carbon-14 dating, which indicate
the numbers of years prior to 1950 (Danjo and Kawasaki 2013b). For OSL and
content analysis, years prior to the time of measurement for OSL and
content analysis were used.
Table 1 Compositions of some beachrocks in the world (Danjo and Kawasaki 2013b)
Component
Component materials of the Main minerals of materials of the
Location beachrock the beachrock cement
Sumuide, Aragonite, Mg Mg calcite
Nago, calcite
Okinawa,
Japan
Sosogi, Sand, gravel, plastic piece, glass Si, Al
Wajima, piece, iron chain
Ishikawa,
Japan
Suzu, Shell sand, foraminifer, sand, Quartz, feldspar, CaCO3
Ishikawa, gravel CaCO3
Japan
Grand Cayman Algae, mollusk, organic material,
coral grains
Heron Island Carbonate grains
Vattakottai, Calcite, aragonite,
India quartz, heavy
minerals
Bozcaada Coarse sand, small gravels of High Mg calcite
Island, Turkey sandstone, basalt, limestone, and
andesite
Siesta Key, Shell fragments 81%, quartz Low Mg calcite
Florida grains 19%, lithoclasts less than
1%
North Uist, Micritic cement 40%, Calcite, aragonite,
Scotland Fragmented shells 30%, Quartz,
Lithoclasts (mainly quartz, Glauconite
Feldspar, glauconite) 30%
Danjo and Kawasaki (2013) compared seven areas with respect to the formative
periods of beachrock: (1) the Aegean coast (Area A); (2) southern India (Area B);
(3) the Great Barrier Reef (Area C); (4) the West Indies (Area D); (5) eastern Brazil
(Area E); (6) the northernmost point, which was Scotland; and (7) the southernmost
point, which was South Africa. They found that the formative periods in
South Africa ranged from several decades ago in Durban to approximately
26,000 years ago around False Bay. There was no distinct concentration of forma-
tions in any one period, and the number of available papers from which data could be
drawn varied significantly depending on the distribution area. Turning next to the
formative period for each distribution area, they also found that the difference
between the length of the formative periods within Area A and Area C could be
quite great, even at the same latitude and longitude. The widest spread in formative
periods for Areas A and C were between approximately 300 and 5,400 years ago and
200 and 6,500 years ago, respectively. These differences in formation times, even
within the same latitude and longitude range, may be attributable to differences in the
AI and Si, 1
Ar and LMC, 1 Silica, 1
LMC, 3
MC and Ar, 9
Aragonite (Ar),
20
Mg calcite
(MC), 9
Ar and
HMC, Ar and
C, 14 Calcite (C), 3
Low Mg calcite
High Mg
(LMC), 2
calcite
HMC and Ar, 6 (HMC), 8
Fig. 4 Beachrock cements around worldwide (Danjo et al. 2013b)
N 50
40
30
20
Latitude (°)
10
10
20
30
S 40
0 2000 4000 6000 8000 10000
Formative age (years ago)
Fig. 5 Formative periods of beachrocks along with latitudes distributed around the world (Danjo
and Kawasaki 2013b)
altitude at which the beachrock was sampled, and there were differences in the
samples. Data were sparse for Area B, and there were only three samples available.
However, the data indicate that formative periods at Area B were concentrated
between 3,100 and 3,700 years ago (Danjo and Kawasaki 2013b). Although there
were few data available for Areas D and E, the data showed that there were large
differences in the formative periods for beachrocks in these areas. In Areas D and E,
the formative periods ranged between approximately 800 and 4,400 years ago and
approximately 200 and 6,900 years ago, respectively (Danjo and Kawasaki 2013b).
For the northernmost area, Scotland, no information was reported on the formative
periods. In the southernmost area, South Africa, the difference in formative periods
was the greatest and ranged from several decades to approximately 26,000 years ago
(Danjo and Kawasaki 2013b).
Origin of Beachrock
Two contrasting theories were proposed regarding the origin of beachrocks: one
cited seawater as the source for beachrocks (Tanaka 1983), and the other claimed that
land-based water such as groundwater or spring water was the source (Yonetani
1963). Therefore opinions were divided between these two theories, but more
support goes to the theory of seawater as the source for beachrock formation (Tanaka
1983).
According to Tanaka (1983), a proponent of the seawater source theory, water
analyses of seawater and groundwater around beachrocks on Otsu Beach and
Yakomo Beach on Okinoerabujima Island showed that the seawater had a higher
content of Ca2+ and a stronger concentration of CO32, while both the seawater and
groundwater had a negative ion charge of 2, which indicates that they had a strong
electrical component in common. Based on these findings, Tanaka claims that the
rising temperature of the water during the day could easily cause the ions in the
seawater to precipitate and form CaCO3.
On the other hand, the theory that groundwater is the source for beachrocks
claims that calcium carbonate precipitates in the surface portion of groundwater form
a cement that enables the surrounding sand particles to consolidate when the
following conditions occur together (Yonetani 1963): (1) when the original ground-
water has a high Ca2+ content, (2) when the groundwater becomes warm due to the
effects of sunlight on the ground surface, and (3) when the pH of the water becomes
high due to the influence of seawater.
Recently, more scientists have expressed the opinion that either of these theories
is possible. The different stable isotopes of seawater and inland water allow the
source of calcium carbonate to be estimated through measurements of stable isotope
ratios (Omoto 2009). After using this method on test samples, Omoto (2009) claims
to have found beachrocks that were formed from both seawater sources and inland
water sources. Meanwhile, Ogasawara et al. (2004) proposed that the presence of
spring water on the mountainous side of Wajima City in the Ishikawa Prefecture in
Japan is strongly connected to the formation of some of the beachrock distributions
in the area.
Theories have also been proposed that assert that living organisms cohabiting in
an area, such as coral, seaweed, sea urchins, starfish, and shellfish, also play a role in
the consolidation of beachrocks (Tachibana 1964; Yonetani 1963). Since living
organisms generate ammonia, inorganic CaCO3 precipitates are formed when sea-
water is added. Furthermore, it has been suggested that landforms, the mixing of
marine and meteoric water, and CO2 degassing can affect beachrock formation
(Danjo and Kawasaki 2013b).
According of Tanaka (1983) and Erginal et al. (2010), the formation process of
beachrocks could be summarized as follows:
Seawater or inland water seeps into the interstitial space between particles of sand
and coral in the intertidal zone and rises to the point where the particles are fully
immersed. Then, the water retreats. With the ensuing exposure to sunlight, calcium
carbonate or silica precipitates consolidate particles together, and as these develop
into aggregates, beachrock is formed (Danjo and Kawasaki 2013b). This scenario
suggests that during the creation of artificial rocks, it will be important to understand
the quality of both seawater and freshwater. However, since the present water quality
at the site of beachrocks that were formed long ago may have changed since the time
of their formation, the investigation of water quality should target recently formed
beachrocks or those that are currently in formation. The details of such a study will
be determined as the present project goes forward.
Artificial Beachrock
Natural beachrocks, which are formed naturally on beaches, have attracted attention
as a model for artificial rocks. Danjo and Kawasaki (2013a) proposed a new method
to protect coastlines from erosion – the use of artificial rock that auto-repairs by
means of sunlight, seawater, and bacteria. Their model of artificial rock is beachrock.
Artificial beachrock is the rock material which is made artificially in the sandy
beaches. Sand particles are particles of coagulated filling voids by precipitation of
carbonate (CO32) of calcium and magnesium where CO32 ion is produced by
bacterial metabolism. By this process cemented sand makes a rocklike material
which is strong and durable like natural rock. As it is made artificially in beach
sand, it is called artificial beachrock.
Formation of Artificial Beachrock
Regarding the origin of beachrocks, two contrasting theories were proposed: one
cited seawater as the source for beachrocks (Tanaka 1983), and the other claimed that
groundwater or spring water was the source (Yonetani 1963). Opinions were divided
between these two theories; and at the time, there was more support for the theory of
seawater as the source for beachrock formation (Tanaka 1983). In this regard Danjo
and Kawasaki (2013a) examined a formation mechanism of beachrock in Okinawa,
Japan; understanding this natural formation mechanism of beachrock is an important
step to making artificial beachrock. They focused on the cement formation mecha-
nism of beachrock, which occurs in the intertidal zone. Cement type and content
have the potential to influence the strength of the material; hence, detailed
B Bacteria
Org. Organic matter
(including urea)
Bacterial ureolysis
Buried beachrock High tide line
Seawater evaporation
B
B
Ca2+ Seawater
B Org. Org.
2+
Ca B Mg2+
Ca2+ B
Low tide line
B B
Coral sand Org. Ca2+
B
Exposed beachrock
Fig. 6 Proposed formation mechanism of beachrock at the study site (Danjo and Kawasaki 2013a)
knowledge of beachrock cements would be valuable for producing an artificial

equivalent (Danjo and Kawasaki 2013a). Beachrocks are cemented by high Mg
calcite (HMC) (Fig. 7) around the world (Erginal et al. 2010). Danjo and Kawasaki
(2013a) focused their investigation into the formation mechanisms of the beachrock
cements on the influence of precipitation from seawater and/or seawater evaporation
(PSW) and on surface microorganisms. Based on formation methods observed for
Okinawa, Japan, artificial beachrock is cemented by HMC using microorganisms
with urease activity, organic matter such as citrate and malate, nutrient sources, CO
(NH2)2, artificial seawater, and sand (Fig. 6) (Danjo and Kawasaki 2014). With
respect to PSW, Raz et al. (2000) reported that to better understand the depositional
process of high-magnesian calcitic skeletons, they studied the CaCO3 precipitates
formed from solutions with Mg/Ca ratios 4. In addition, sodium citrate and sodium
malate favor the precipitation of MC, whereby an increase in concentration of
magnesium ion and these organic materials causes the formation of Mg-rich calcite
(Khan and Kawasaki 2015).
Bio-cementation
Bio-cementation Technique
Chemical cementation (or chemical grouting) process is used to fill the sand voids
with fluid chemical grouts to produce sandstone-like masses to carry loads. This
chemical cementation method is widely used in geotechnical engineering. The
chemicals that are used to bind soil particles include sodium silicate, calcium
Biological
process (BIOL)
and Physico/ Listedness, 3
chemical
factors (P/C-F),
1
Precipitation
from seawater
and/or marine
Precipitation water
from fresh evaporation
water (PFW), 1 (PSW), 10
Sea - fresh
water mixing
(S-FWM), 1
Fig. 7 Formation mechanisms of beachrock whose cements contain high Mg calcite (Danjo et al.
2013b)
chloride, calcium hydroxide (lime), cement, acrylates, acrylamides, and polyure-

thanes (Karol 2003).
Bio-cementation (or microbial cementation) is a cementation process in which
sand particles are coagulated using the metabolic activities of microorganisms.
Microbial cementation is to form soil particle-binding material after the introduction
of microbes and specific additives into soil. In this method precipitation of carbonate
(CO32) of calcium, magnesium, etc., is used to fill the sand voids where CO32 ion
is produced by bacterial metabolism. Urea-producing bacteria are used in this
process mainly. It is different from biobinding, which is the formation of the
particle-binding cellular chains (Ivanov and Chu 2008). Biobinding can be
performed by mycelial fungi, actinomycetes, and filamentous phototrophic and
heterotrophic bacteria (Ivanov and Chu 2008). In some experiments, the added
biomass of some fungal strains binds the sand grains and increases the shear strength
of soil (Meadows et al. 1994). However, biobinding does not seem to be suitable for
large-scale operations such as enhancing the liquefaction resistance of land recla-
mation sites due to its instability of biological bindings, and it can be degraded by
other microorganisms (Ivanov and Chu 2008).
Chemical cementation of soil in nature is due to the precipitation of material in
spaces between soil particles and binding of these particles together into a hard
rock. Microorganisms are often associated with the cemented sediments,
containing calcium, magnesium, iron, manganese, and aluminum, which are
crystallized as carbonates, silicates, phosphates, sulphides, and hydroxides, espe-
cially iron hydroxides (DeJong et al. 2006). Chemical transformations of metals
and ions in soil or sand are mediated by soil microorganisms. An example of sand
cementation in nature is the formation of ferrihydrite in pores (Ross et al. 1989).
Iron hydroxides, depending on its crystallization, can be also an important
cementing agent in soils (Duiker et al. 2003). Drying of soil samples containing
iron hydroxide can produce irreversible soil hardening and cementation (Ivanov
and Chu 2008).
An example of natural cementation is the precipitation of silica dioxide, which
fills in the pores and glues the soil particles together (Ivanov and Chu 2008). It is also
known as natural soil calcification due to the deposition of calcium carbonate from
upward flow of groundwater, enhanced evapotranspiration from soil, or formation of
calcium carbonate within zones of elevated carbonate alkalinity formed by microbial
decay of organic matter (Mozley and Davis 2005).
In a patent, Kucharski et al. (2005) applied microbial bio-cementation
for the formation of high strength cement in a permeable material using the
combination of this material with biomass of urease producing microorganism,
urea, and soluble calcium salts. Microorganisms provide fast urea hydrolysis,
increase the pH during hydrolysis of urea to ammonia, and form calcite in
soil or rocks. The cement produced has a compressive strength up to
5 MPa. The materials, treated by bio-cementation, may be conglomerate,
breccia, sandstone, siltstone, shale, limestone, gypsum, peat, lignite, sand,
soil, clay, sediments, and sawdust. The urease-producing microorganisms are
from genera Bacillus, Sporosarcina, Sporolactobacillus, Clostridium, and
Desulfotomaculum.
This method of microbial cementation could be used for the following civil and
environmental engineering applications (Kucharski et al. 2005):
• Controlling erosion in coastal area and rivers

• Enhancing stability for retaining walls, embankments, and dams
• Reinforcing or stabilizing soil to facilitate the stability of tunnels or underground
constructions
• Constructing a permeable reactive barrier in mining and environmental
engineering
• Increasing the bearing capacity of piled or non-piled foundations
• Reducing the liquefaction potential of soil
• Treating pavement surface
• Strengthening tailing dams to prevent erosion and slope failure
• Binding of the dust particles on exposed surfaces to reduce dust levels
• Increasing the resistance to petroleum borehole degradation during drilling and
extraction
• Increasing the resistance of offshore structures to erosion of sediment within or
beneath gravity foundations and pipelines
• Stabilizing pollutants from soil by the binding
• Creating water filters and borehole filters
• Immobilizing bacterial cells into a cemented active biofilter
Microbially Induced Carbonate Precipitation (MICP)
In bio-cementation process calcium carbonate (CaCO3) or other carbonates is

precipitated using microorganism to join sand particles. As carbonates are precipi-
tated using microorganism, it is known as microbially induced carbonate precipita-
tion (MICP). Like other biomineralization processes, calcium carbonate (CaCO3)
precipitation can occur by two different mechanisms: biologically controlled or
induced (Lowenstan and Weiner 1988). In biologically controlled mineralization,
the organism controls the process, i.e., nucleation and growth of the mineral parti-
cles, to a high degree. The organism synthesizes minerals in a form that is unique to
that species, independently of environmental conditions. Examples of controlled
mineralization are magnetite formation in magnetotactic bacteria (Bazylinski et al.
2007) and silica deposition in the unicellular algae coccolithophores and diatoms,
respectively (Barabesi et al. 2007). However, calcium carbonate production by
bacteria is generally regarded as “induced,” as the type of mineral produced is
largely dependent on the environmental conditions (Rivadeneyra et al. 1994), and
no specialized structures or specific molecular mechanism are thought to be involved
(Barabesi et al. 2007). Different types of bacteria, as well as abiotic factors (salinity
and composition of the medium), seem to contribute in a variety of ways to calcium
carbonate precipitation in a wide range of different environments.
This approach mimics natural processes (Eqs. 1 and 2) by depositing calcite
(CaCO3) on the soil grains, thereby increasing the material’s stiffness/strength and
reducing its erodibility. The microbiological process relies on ureolytic (nonpatho-
genic) bacteria such as Sporosarcina pasteurii or Bacillus pasteurii to hydrolyzed
urea in the presence of calcium ions, resulting in the precipitation of calcite crystals.
Urease
COðNH2 Þ2 þ 2H2 O ! 2NH4 þ CO3 2 (1)
yields
Ca2þ þ CO3 2 ! CaCO3 ðsÞ (2)
The actual role of the bacterial precipitation remains, however, a matter of debate.
Some authors believe this precipitation to be an unwanted and accidental by-product
of the metabolism (Knorre and Krumbein 2000), while others think that it is a
specific process with ecological benefits for the precipitating organisms
(Ehrlich 1996).
The Role of Urease Activity in Carbonate Precipitation
Urease
Urease was the first enzyme to be isolated in its crystalline form from Canavalia
ensiformis (jack bean) (Sumner 1926). The first three-dimensional structural model
of urease was observed by X-ray of a bacterial source, Klebsiella aerogenes (Jabri
et al. 1995). Kl. aerogenes urease consists of four domains, one of which contains an
active site with a bimetallic nickel center. These primary structures of Kl. aerogenes
and Sporosarcina pasteurii (formerly known as Bacillus pasteurii) urease are iden-
tical (Mulrooney and Hausinger 1990). Urease is synthesized under the condition of
nitrogen starvation (Mobley et al. 1995). There are contradictory statements regard-
ing the location of urease in the bacterial cells. The urease is located in the membrane
and periplasm of Staphylococcus sp. and Proteus mirabilis (McLean et al. 1986).
Mechanism of Urease Reaction

Urea is released into the environment due to biological action, for example, all
mammals excrete urea as a detoxification product. Urease (urea amidohydrolase; EC
3.5.1.5) is widely distributed in soil and aquatic environments. Biotic urease activity
is widespread in the environment and includes the action of bacteria, yeasts, fila-
mentous fungi (Mulrooney and Hausinger 1990), algae (Yates and Robbins 1999),
and a number of higher plants including jack beans (Canvalia ensiformis), soybean
leaf and seed (Glycine max), pigweed (Chenopodium album), and mulberry leaf
(Morus alba) (Al-Thawadi 2011).
Urease hydrolyzes the substrate urea generating ammonia and carbamate (Eq. 3).
Carbamate spontaneously decomposes to produce another molecule of ammonia and
carbonic acid (Eq. 4) (Mobley and Hausinger 1989). The two ammonia molecules
and carbonic acid subsequently equilibrate in water with their deprotonated and
protonated forms, resulting in an increase in the pH (Eqs. 5 and 6) (Mobley and
Hausinger 1989).
Urease
COðNH2 Þ2 þ H2 O ! NH3 þ COðNH2 ÞOH (3)
COðNH2 ÞOH þ H2 O ! NH3 þ H2 CO3 (4)
H2 CO3 $ HCO3 þ Hþ (5)
2NH3 þ 2H2 O ! 2NH4 þ þ 2OH (6)
Cementation Process Through Bacterial Action
Bacterial CaCO3 precipitation under appropriate conditions is a general phenome-

non (Boquet et al. 1973). There are a number of species of CaCO3 minerals
associated with bacteria, for example, vaterite formation by Acinetobacter
sp. (Sanchez-Moral et al. 2003), aragonitic spherulites by Deleyahlophila
(Rivadeneyra et al. 1996), calcite by E. coli (Bachmeier et al. 2002), and magnesium
calcite spherulites and dumbbells by the slime-producing bacteria, Myxococcus
xanthus (González-Muñoz and Chekroun 2000). One of the most robust ureolytic
bacteria is S. pasteurii. It is an aerobic, spore-forming, rod-shaped bacterium. It uses
urea as an energy source and produces ammonia which increases the pH in the
environment and generates carbonate, causing Ca2+ and CO32 to be precipitated as
Fig. 8 Schematic model for (1) Organic substrate

cement precipitation (Urea)
(Al-Thawadi 2011)
Cell
Low pH (6.8) Ca2+ (3)
EPS
HCO3–
Micro-environment
NH4+ CO3–
(2) High pH
(9.2) (4) CaCO3
CaCO3 (Eqs. 7, 8, and 9) (Stocks-Fischer et al. 1999). Alkaline pH is the primary

means by which microbes promote calcite precipitation (Fujita et al. 2000). Based on
various studies, a schematic model describing the role of ureolytic bacteria on
calcium carbonate precipitation is illustrated in Fig. 8 (Al-Thawadi 2011).
Ca2þ þ Cell ! Cell Ca2þ (7)
Cl þ HCO3 þ NH3 $ NH4 Cl þ CO3 2 (8)
Cell Ca2þ þ CO3 2 ! Cell CaCO3 # (9)
The schematic model (Fig. 8) is summarizing the role of ureolytic bacteria in

CaCO3 precipitation in the presence of Ca2+ ions. The processes involved in CaCO3
precipitation are (1) hydrolysis of urea (Eqs. 3, 4, and 5), (2) increasing the alkalinity
of the microenvironment (Eq. 6), (3) surface adsorption of Ca2+ions (Eq. 7), and
(4) nucleation and crystal growth (Eqs. 8 and 9). EPS stands for extra polysaccharide
in the case of the presence of EPS surrounding the ureolytic cells.
There are two metabolic pathways for bacterial carbonate formation. These
pathways are autotrophic and heterotrophic pathways (Al-Thawadi 2011). Regard-
ing autotrophic pathway, CO2 is used as a carbon source causing its depletion in the
bacterial environment. In the presence of Ca2+ ions, such depletion enhances the
production of CaCO3.
Regarding heterotrophic pathways, bacteria can precipitate CaCO3 through active
or passive precipitation. In active precipitation, the production of CO32 is due to
ionic exchange through the cell membrane by calcium and/or magnesium ionic
pump. During passive precipitation, the production of CO32 is due to ammonifica-
tion of amino acids, dissimilatory reduction of nitrate, or degradation of urea or uric
acid. In all cases, ammonia as a metabolic end product is produced which induces a
pH increase.
CaCO3 precipitation rate in general is a linear function of the ion concentration
product of (Ca2+) and (CO32) hence obeying second-order kinetics or first-order
kinetics if one of the reactants (e.g., calcium) is in excess (Al-Thawadi 2011).
Different rate constants have been obtained for bacterial CaCO3 precipitation
(Table 1).
Applications of Carbonate Precipitation Through Bacteria
The evidence of microbial involvement in carbonate precipitation has subsequently

led to the exploration of this process in a variety of fields. A first series of
applications is situated in the field of bioremediation. In addition to conventional
bioremediation strategies which rely on the biodegradation of organic pollutants
(Chaturvedi et al. 2006), the use of MICP has been proposed for the removal of metal
ions. Applications include the treatment of groundwater contaminated with heavy
metals and radionucleotides, the removal of calcium from wastewater, etc. Another
series of applications aims at modifying the properties of soil, i.e., for the enhance-
ment of oil recovery from oil reservoirs and plugging and strengthening of sand
columns. Moreover, microbially induced precipitation has been investigated for its
potential to improve the durability of construction materials such as limestone and
cementitious materials.
Bacterial CaCO3 formation through urea hydrolysis is known as bacterial calcite
precipitation (BCP). BCP is highly desirable because it is natural and pollutant-free.
There are several applications for BCP, most of which are considered for purposes
other than strength development (Al-Thawadi 2011). Some of these applications are
the (1) removal of contaminants (e.g., radioactive pollutants) and calcium ions from
groundwater and wastewaters, (2) protection and restoration of limestone monu-
ments and statuary, (3) creation of sacrificial patinas on limestone and production of
biological mortars or cements, (4) plugging the pores of the oil-recover reservoir
rock, and (5) stone formation or sand cementation. Below are more details of these
applications.
Contaminants Removals from Groundwater and Wastewater

The capturing of divalent radionucleotide Strontium 90 (90Sr2+) in the groundwater
was investigated after the addition of high concentration of urea and very low
concentration of Ca2+ ions (Fujita et al. 2000). Strontium carbonate (90SrCO3)
was precipitated, in such a way that (90Sr2+) replaces Ca2+ ions in the calcite crystal
preventing the spread of radionucleotide contamination.
The potential of removing Ca2+ ions from industrial wastewaters facilitated by
BCP instead of chemical precipitation was studied (Hammes et al. 2003). The
presence of a high concentration of calcium ions (500–1500 mg.L-1) in the waste-
water causes severe scaling in the pipelines and reactors due to calcium formation as
carbonate, phosphate, and/or gypsum. By the addition of a low concentration of urea
(0–16 g.L-1), up to 90% of the calcium ions were removed from the examined
wastewater.
Protection and Restoration of Monuments and Creation of Biological

Grouts
Physical, biological, and chemical factors may cause the weathering of monumental
stones. Construction materials, for example, are exposed to Cl, SO42, CO2, and
atmospheric moisture which react with the surface layer or penetrate inside the
materials (Chunxiang et al. 2009). Consequently, a loss of cohesion of stone
material, progressive mineral matrix dissolution, and micro-cracks formation will
be enhanced (Chunxiang et al. 2009). In the case of calcareous stones, the porosity
will increase due to CaCO3 leaching and weakening of the superficial structure of the
stone (Tiano et al. 1999). The attempt which was done by Tiano (1999) in stopping
or slowing down the deterioration of monumental statuary by ureolytic bacteria was
successful in surface coating but not strength production, as no significant difference
in strength was recorded after CaCO3 precipitation. In a recent study, a new layer of
CaCO3 was precipitated on the surface of an old concrete layer by S. pasteurii
(Al-Thawadi 2011). It was concluded that cracks remediation may enhance the
strength and the durability of the concrete.
Plugging the Pores of the Rock

Bacterial cells were used to plug the highly permeable rocks of the oil reservoir.
Between 8% and 30% of the total oil present in oil reservoir was recovered from
ordinary oil production method (Al-Thawadi 2011). Oil recovery depends on pri-
mary and secondary treatments (water flood) to recover the crude oil in the pores of
the reservoir rock (Bryant 1987). To improve the recovery method after primary and
secondary treatments, conventional methods depending on chemical or thermal
energy are used. These conventional methods are considered inefficient as they led
to 67% retention of the total oil within the pores of the reservoir rock (Bryant 1987).
Therefore, there was an interest in the use of microbes to enhance the oil recovery.
This use of microbes can be through microbial production of bio-surfactants and
biopolymers at the surface; microbial growth in the pores of the oil reservoir rocks
producing gasses, surfactants, and other chemicals; or microbial plugging of the
pores in the oil reservoir channels, which may result in increasing the sweeping
effectiveness of the recovery process.
The rocks of the oil reservoir contain high permeability zones. When the water is
injected to displace oil, it will move through the pores of the highest permeable zone,
bypassing much of the oil. Because of the small size of the bacteria, they will move
to highly permeable areas, plugging the pores, and as a consequence, the sweep
efficiency and oil recovery will be enhanced up to 100% (Bryant 1987).
In the ordinary method of bacterial enhancement of oil recovery, plugging of the
pores was due to bacterial multiplication, production of gasses that increases the
pressure, and production of organic acids, surfactants, and polymer (Al-Thawadi
2011). Much attention is devoted to the plugging of highly permeable zone via
bacterial urea hydrolysis. This type of plugging probably offers a feasible alternative
to block the rock pores, improving the residual oil recovery. Complete plugging
within days was achieved by mixing bacteria with sand before packing into cores
followed by the application of calcium, urea, and carbonate (Gollapudi et al. 1995).
Moreover, it was found that the bacteria plug the sand granules by providing a
nucleation site at which CaCO3 was precipitated through alkaline environment
(Stocks-Fischer et al. 1999).
Sand Cementation Through Bacterial Carbonate Precipitation
Bio-cementation or biogrout is a sand consolidation technology, in which ureolytic

bacteria release carbonate from urea hydrolysis in the presence of an excess of
calcium ions to form calcite (CaCO3) in situ. Under the proper conditions, this
calcite can result in soil solidification and has found significant commercial interest
(Al-Thawadi 2008). In geotechnical engineering, the sandstone is produced by
filling the sand voids with chemical grouts in a process called chemical cementation
or chemical grouting (Al-Thawadi 2011).
Chemical cementation depends on chemicals such as sodium silicate, calcium
chloride, calcium hydroxide (lime), cement, acrylates, acrylamides, and polyure-
thanes to bind the sand granules (Al-Thawadi 2011). Construction materials
cemented chemically are subjected to weathering which leads to increase the poros-
ity changing the mechanical features of the cemented materials (Tiano et al. 1999).
Bio-cementation could be greatly enhanced by using microorganisms with high
urease enzyme activities indirectly involved in CaCO3 consolidation (Stocks-Fischer
et al. 1999). Besides the high urease activity, a high tolerance to urea, calcium,
ammonium, and either nitrate or chloride (depending on the calcium salt used)
enhances the bio-cementation (Whiffin et al. 2007).
There is a lack of knowledge regarding the high strength production of the
bio-cemented products (sandstone formation). Most of the CaCO3 precipitation
studies achieved a consolidation or patching treatments for existing material as
described previously. Sandstone production depends on how strong the binding
between the sand particles, which affects the cementation quality of the precipitated
calcite.
The growth of CaCO3 crystals for the purposes of artificially cementing sedi-
ments proved difficult because of the low yields obtained from a number of different
reactions at room temperature. However, the successful bonding of calcareous
sediments with derivatives of aluminum alkoide indicates that CaCO3 is a promising
route to stabilize loose particles (Al-Thawadi 2011). Superior to this sediment
cementation attempt, the loose particles were well cemented by chemical precipita-
tion of CaCO3 through calcite in situ precipitation system (CIPS), producing high
degrees of calcite cementation similar to the natural sediments within less than 24 h.
This CIPS technology (a non-microbial cementation process) is similar to the natural
process that forms the rocks (Joer et al. 2002). This successful rock formation by
chemical CaCO3 precipitation indicates a great deal of scope for further work on the
strength of microbiological CaCO3 precipitation in a porous medium.
Nemati and Voordouw (2003) have described the use of urease to cement a
porous medium. In this study, reducing the permeability of a porous medium by
enzymatic CaCO3 precipitation through Canavalia ensiformis was achieved. Nemati
and Voordouw used between 0.1 and 1.0 M (>33 g.L-1) calcite together with high
urease activity for a successful plugging of the sand core. Unfortunately, the strength
buildup was not monitored.
The study of Whiffin (2004) was the first published study in bacterial plugging of
loose sandy material through urea hydrolysis (biogrout) for the purpose of strength
production. She used P. vulgaris and S. pasteurii during her study. This study was
successful in producing strength of 1.8 MPa which was achieved through three
applications of bacterial cells and cementation solution. Whiffin (2004) has
established a bio-cementation method which depends on a fast flow rate to inject
the bio-cementation mix (bacteria, calcium, and urea). The fast flow rate is not
recommended to consolidate fine sands. The used cementation solution (calcium/
urea) ranged between 0.75 and 1.5 M. In some cases Whiffin (2004) has recorded a
full precipitation of calcite within 18 h. Due to the calcite precipitation, which blocks
the pores, a low penetration depth (maximum of 170 mm, i.e., penetration depth
is the distance along a packed sand column which can be penetrated by bacterial
cells and cementation solution to cement the sand granules) was achieved. Beside
this low penetration depth, the inconsistency of urease production by P. vulgaris
and S. pasteurii is considered to be another problem which has arisen throughout
her study.
Al-Thawadi (2008) developed successfully the use of biological cementation to
produce high strength comparable to that of the traditional cemented construction
materials such as sandstone and concrete with high penetration depth. This study
developed a method of producing high strength cemented sandy materials (up to
30 MPa, equivalent to construction cement) through bacterial hydrolysis. This high
strength production was achieved without a significant decrease in the permeability.
Moreover, high penetration depth up to 1 m was achieved. Al-Thawadi (2008)
suggested that the mechanical strength enhancement of cemented sandy materials
was caused mostly due to the point-to-point contacts of rhombohedral CaCO3
crystals and adjacent sand grains (Fig. 9). These bridges will bind the sand granules
together and increase strength and stiffness (Al-Thawadi 2008).
Inhibition of Coastal Erosion Through Artificial Beachrock
Coastal erosion is the removal of beach or dune sediments naturally such as wave
action, tidal currents, wave currents, drainage or high winds, and/or man-made
activities as tourism, civil constructions, etc. Waves, generated by storms, wind, or
fast-moving motor craft, can cause coastal erosion, which may take the form of long-
term losses of sediment and rocks or merely the temporary redistribution of coastal
sediments; erosion in one location may result in accretion nearby.
To preserve coastlines, various countermeasures are used to combat coastal
erosion. These include construction of artificial reefs, headlands, detached
Fig. 9 Light microscopic

image for calcite crystals
produced by ureolytic bacteria
binding two sand particles
(Al-Thawadi 2008)
breakwaters, and hard shore protection, all of which control the amount of drift sand
and/or beach nourishment and sand bypassing, thus overcoming shortages of drift
sand. However, these solutions are expensive and require long-time periods for
implementation, as well as the engineering of large amounts of materials, especially
for heavyweight sand coasts. The maintenance and management for repair and
rebuild the coast are expensive. As a hint for an alternative material in order to
reduce life-cycle costs, it is focused on the beachrock.
The cement component of beachrocks mainly consists of either calcium carbonate
or silica. By utilizing the process of forming the beachrock than to solidify the beach
sand, it is considered to be possible to create a highly durable with self-healing
capabilities artificial beachrock comparable with existing concrete structures. Com-
pared to the concrete structure, coral sand solidification would be considered to
minimize cost. Bio-cementation technology is used to making artificial beachrock.
Therefore, it may be possible to slow down the erosion of coasts by making
man-made beachrock from coastal sands. Because this artificial rock is made of
local materials, it has the potential to be an eco-friendly product (Danjo and
Kawasaki 2013a).
Conclusion
In the future, it may be possible to manufacture artificial rocks similar to beachrocks

for erosion control purposes. Manufacturing of artificial beachrocks using compo-
sitional substances are possible as similar to those in beachrocks, and that follow the
same formation process. Although bio-cementation technology is a promising tech-
nology due to its suitability to field application, it also may results in an environ-
mental problem due to its high production of high concentration of ammonium
during urease activity.
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Potential of Biogas Technology
in Achieving the Sustainable 58
Developmental Goals: A Review
Through Case Study in Rural
South Africa
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1424
Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1426
Case Study Area Presentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1426
Use of Existing Case Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1426
Questionnaire . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1426
Questionnaire Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1427
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1427
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1431
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1431
Abstract
More than half of the Sustainable Development Goals’ (SDGs) target group are
rural poor dwellers from developing countries, particularly in Asia and Africa, who
normally live on subsistence agriculture. Thus, securing a productive and profitable
agricultural sector for the rural areas becomes a fundamental component in accel-
erating the achievement of the SDGs by 2030. One in eight people worldwide still
remain hungry and under poverty. So this paper reviews progress in the achieve-
ment of the SDGs in rural South Africa and the potential role appropriate technol-
ogies played and/or could play, in particular biogas technology, in the achievement
of these SDGs. Questionnaires, interviews, field trips, and community engagement
T. E. Rasimphi (*) · W. M. Gitari

Department of Ecology and Resource Management, University of Venda, Thohoyandou,
South Africa
e-mail: eugenethilivhali@yahoo.com; mugera.gitari@univen.ac.za
D. Tinarwo
Department of Physics, University of Venda, Thohoyandou, South Africa
e-mail: david.tinarwo@univen.ac.za

https://doi.org/10.1007/978-3-319-73645-7_40
1424 T. E. Rasimphi et al.
were used to establish both the baseline and the impact of biogas use in the
improvement of livelihood. Through the use of the biogas technology, agricultural
production was improved, and all the chemical fertilizer was replaced by bio-slurry
from the digestion process. More economic activities were witnessed through
enlargement of the crop farming to make use of the produced slurry raising the
need of additional manpower and thus enhancing economic opportunity by creating
jobs in the sector. A fair reduction of pressure on local forests was witnessed in the
case studied. Thus the use of biogas has impacted positively to the accelerated
achievement of some of the SDGs in the communities studied, and this technology
presents real solution to the sustainable development of poor communities.
Keywords
Sustainable rural development · Renewable energy technologies · Sustainable
development · Sustainable development goals · Biogas
Introduction
In the absence of new energy policies, the number of people depending on biomass
will rise to over 2.6 billion by 2015 and to 2.7 billion by 2030 because of population
growth (World Energy Outlook 2016). That is, one-third of the world’s population
will still be relying on these fuels. There is evidence that, in areas where local prices
have adjusted to recent high-energy prices, the shift to cleaner, more efficient use of
energy for cooking has actually slowed and even reversed. According to the report
on energy for cooking in developing countries, it was stated that the UN Millennium
Project adopted a target of reducing by 50% the number of households using
biomass as their primary cooking fuel by 2015 (UN Millennium Project 2005).
The appropriate choice of energy source will vary by country, by region, and over
time, for example, ethanol gel, plant oils, and biogas. Some communities will prefer
the cleaner, more efficient use of biomass energy (World Energy outlook 2016).
Large-scale substitution of traditional biomass by alternative fuels will need to take
place as well. Meeting the 2015 target would mean 1.3 billion people switching to
cleaner alternative energy sources as their primary fuel, while universal access in
2030 would call for 2.7 billion people to switch (IEA 2015).
Biogas technology is growing steadily even in countries like South Africa, where
there is energy poverty (Amigun and Von Blottnitz 2009). Biogas potential as a
renewable energy is magnificent for cooking in rural areas, but currently it is not
used as expected. Greben and Oelofse 2009, suggested that as biogas is considered a
renewable energy, it can contribute to the South African government’s 10-year goal
of promoting renewable energy biogas technology installations which are taking
place yet at a very minimal level. There is positive response to the renewable energy
sector especially for those who know the benefits of the technology. Poor access to
recent energy supplies and unsustainable practices in rural areas of South Africa
have been causing environmental destruction and health risk to users (Gender and
Sustainable Development Report 2016).
58 Potential of Biogas Technology in Achieving the Sustainable. . . 1425
Over the past quarter century, there has been impressive progress on many fronts
in human development, with people living longer, more people rising out of extreme
poverty, and fewer people being malnourished (Human Development Report 2016).
Human development has enriched human lives – but unfortunately not all to the
same extent and even worse, not every life. It is thus not by chance but by choice that
world leaders in 2015 committed to a development journey that leaves no one out – a
central premise of the 2030 agenda.
According to the Human Development Report (2016), there is already tremen-
dous progress in the achievement of the SDGs, and this has been considered the most
successful antipoverty push in the history with already the poverty reduction target
reached through the Millennium Development Goals, though many areas are still
lagging behind. Environmental sustainability is under severe threat, demanding a
new level of global cooperation (Ensuring Environmental Sustainability 2005). By
large, the poorest people and the poorest countries are the most affected by envi-
ronmental degradation. Indoor air pollution, caused by smoke from stoves and fires,
causes around 1.6 million deaths per year in developing countries (World Health
Organization 2002).
The problem requires urgent strategies to protect the environment, to achieve
economic development, and to increase social transformation, for example, the living
environment is improved by eliminating dirty sources of energy, and by-product like
ash is eliminated. The smoke is no longer a problem to the biogas user and the living
conditions are now improved (Hornberg and Pauli 2007). It is impossible to imagine
major progress in reducing poverty without expanding access to modern energy by the
poor, who still rely on dangerous and highly polluting traditional fuels, such as cow
dung and wood residues. The International Energy Agency estimates that investments
of about USD 17 billion per year over 12 years will be needed to provide an additional
500 million people with access to electricity by 2015 (UNDP et al. 2005).
Economically, biogas technology comes with financial benefits, for instance, the
money which was supposed to be used to buy electricity and other sources of energy
is saved (Smith et al. 2013). The economic status of the household is improved.
During construction there is skills development when the local residents are taught
how to build, install, and use the biodigester. It is also simple to use because less time
is spent on using the digester compared to using traditional methods of energy. Thus,
a solid and current research based on primary data is needed in order to properly
qualify and quantify the potential benefits technically, socially, economically, and
environmentally of this technology at the rural household level.
For successful implementation of biodigester, there must be availability of organic
wastes. Rural are known to generate a lot of organic waste through household activity
and farming (UNDP et al. 2005). However, rural areas of developing countries are
dependent on primary sources of energy such as firewood and dried dung as sources of
energy (O’Neill et al. 2009). Using primary energy sources is often coupled with many
environmental problems such as deforestation, land degradation, and various health
and social problems as well as emissions of greenhouse gases (Karekezi 2002). Thus
the use of biomass as feedstocks to biodigester would reduce fuelwood collection and
save money which are some of the benefits of using biogas technology.
Organic waste-to-energy conversion brings much needed benefits for rural people
such as clean heat, smokeless environment in the kitchen, and in some cases even
electricity (Amigun and Von Blottnitz 2007). This effectively reduces reliance on the
grid electricity whose cost is unsustainable for rural communities. On an economic
level, biogas technology makes a contribution toward national economic develop-
ment in that some employment will be created during construction, installation, and
maintenance of digesters. Moreover income generated improves the people’s stan-
dards of living, hence the eradication of historical economic imbalances.
Objectives
To demonstrate the potential of biogas technology in achieving Sustainable Devel-

opment Goals. Main indicators that have been used include crop production, women
involvement, and environmental sustainability.
Case Study Area Presentation
The study focused on assessing the potential of biogas in achieving sustainable

development goals in Vhembe District.
Use of Existing Case Studies
Although the use of extrapolation and benefit transfer models, especially with regard
to stated preference results, is generally not favored (Pearce and Ozdemiroglu 2002),
desk research is easy and quick. In the case of this research, where time and
resources are not without limits, it appears to be acceptable to make provision for
extrapolation and use of aggregate regional data when site-specific details are not
available (European Commission 2002). Information was gathered from journals,
research studies, library database, and the study sites. This involved case studies on
biogas technology utilization in Vleifontein. Census 2011 rated Limpopo Province
as the poorest in the country with a head count poverty level of about 63.8% (Lehlola
2014) and yet with one of the best agricultural climate and vast natural resources.
Questionnaire
In order to conduct a comprehensive feasibility study of the potential benefits of rural

household biodigester use (Smith et al. 2013), it was necessary to first bring
information about the current characteristic and energy demands of rural household
in the study area. For this purpose a questionnaire was designed to gather detailed
information about the household, their energy requirement, their livestock keeping
practice, water usage, and the production of crops and vegetables at their home-
steads. The questionnaire design, survey, and analysis process is discussed in the
preceding section.
Questionnaire Design
The questionnaire used in this research was based on and adapted from previously
used questionnaire: a questionnaire used in a biomass energy audit conducted by
Rhodes University and a biogas perception and behavior questionnaire conducted by
Agama Energy and Jabezi in the development of the South African National Biogas
feasibility study (Austin and Blignaunt 2008; Smith 2013). The questionnaire was
used as a basis for this research project as they had been tried and tested in the field
and had contributed to save meaningful studies (Smith 2013).
Results
Theoretically any type of biomass can be degraded to biogas; the growth of biogas
technology has caused the use of cow dung, chicken manure, and organic waste to be
used. Cow dung is especially suitable because of the methanogens in the stomachs of
the ruminants (Bond and Templeton 2011). The dung produced by cattle per day per
animal is about 10 kg, and 1 kg of cattle is not pastured at the cooperative; it was
assumed that collectable waste per kg per day is about 10 kg, and 1 kg of cattle
produces 0.0036 m3 of biogas (Nijaguma 2002). Since the cattle are not pastured at
the cooperative, it was assumed that collectable waste per kg per day was 5 kg. In
addition, 1 kg of chicken manure wastes produce 0.062 m3 (Mukumba et al. 2013).
The installed digester reduced the dependence of the cooperative from fuelwood and
LPG which they used for cooking.
Marubini Women’s Multi-purpose Co-operative is a women’s’ cooperative in
Maila Village, Makhado in the northernmost province of Limpopo in South Africa.
Census 2011 rated Limpopo Province as the poorest in the country with a head count
poverty level of about 63.8% (Lehlola 2014); it has the best climate for agriculture
and vast natural resources. The cooperative was established in 1995 as a nonprofit
organization by unemployed women and was engaged in mushroom production. The
group was then encouraged to register as a cooperative, a development organization
registered with the Department of Health and Social Development as a nonprofit
organization. The cooperative has a membership of 12 (permanent cooperative
members) and 10 volunteers. Its main activities are early childhood development
with 250 children at crèche level. Besides running this crèche, the cooperative also
do poultry production at a capacity of around 3200 egg layers at a time throughout
the year (Tinarwo et al. 2014). The cooperative is also in cash crop production. The
place is now a well-known site with a lot of visitors coming for different reasons
ranging from business, buying the produce, to even learning purposes.
The cooperative uses a lot of energy in the form of heat to cook food for children.
They get firewood supplies from local entrepreneurs who charge exorbitant prizes.
On the other hand, they produce a lot of waste from the egg layers which can be used
to feed the biodigesters, and the waste poses disposed challenge in addition to the
health issues.
The cooperative is very satisfied with the benefits demonstrated by including the
bioenergy system in their farming activities. Although it is still too early to make
definite assumptions on all benefits, the cooperative already is saving R925 (has
been realized from cooking energy only). On the agricultural part, the yields have
improved significantly in both quantity and in quality as a result of the use of
bio-slurry as fertilizer. The unpleasant odor from chicken wastes has significantly
been reduced with the use of biodigester. After realizing the great potential of
production of energy from biogas, with more waste use, the cooperative already is
working toward expanding the number of egg layers quantity and increasing the crop
farming sector now that fertilizer is available (Tinarwo et al. 2014).
This cooperative is now used by the university project team to disseminate
information to other stakeholders and to others users. Field days are regular at the
project site with day-long workshops carried out on site giving other great opportu-
nities of catering services to participants. The place has turned to be a center of
attraction, receiving all kinds and levels of visitors with even local and provincial
government leadership visiting to see a working self-sustaining integrated agricul-
tural bioenergy system.
Biogas technology played an important role in improving the quality of life for
the cooperative since it was introduced. In addition to being a renewable source of
energy that is locally available, biogas has an extensive range of additional benefits
to people. Some of these benefits include:
(a) More hygienic conditions, thanks to the elimination of indoor air pollution from
fuelwood, which is particularly harmful to women who are responsible for
cooking.
(b) Preventing deforestation by reducing the detrimental harvesting of trees as fuel-
wood. Maila cooperative used fuelwood for cooking food for the children, and the
introduction of biogas has lessened the reliance on wood as energy source.
(c) Burning biogas is cleaner than burning fuelwood. Apart from being smokeless,
the only emissions are carbon dioxide and water; thus carbon emission to the
atmosphere is reduced.
(d) Macroeconomic benefits such as job creation thanks to the staffing needs of
biogas plant construction. The cooperative enjoys the benefits from their sales of
agricultural practices like cabbage, pumpkin, and spinach (see Fig. 1).
Biogas technology offers an exceptional set of benefits (Fig. 1). It improves the
health of users, it is a sustainable source of energy, it benefits the environment, and it
provides a way to treat and reuse various wastes: animal and agricultural (Tinarwo
et al. 2014).
Fig. 1 Potential of biogas technology to improve household energy users lives (Tinarwo
et al. 2014)
Whilst there is a common agreement that rural communities urgently need to

increase their access to current energy sources (World Bank 2000), fuelwood use has
an impact on the social and economic status of rural community as it is considered
the primary energy source, and all cooking activities depend on fuelwood.
Majority of rural households in South Africa are still dependent on firewood and
paraffin (Shackleton et al. 2007). This is evident from the questionnaire survey
conducted in the study area that large percentages still depend on fuelwood for
cooking and heating.
The acquisition of fuelwood is a major cost in a resource-poor household, be it in
terms of time and energy. Although this study did undertake an analysis on time
constraint for collection of fuelwood from the nearby forests. Other studies have
been adopted to highlight time collection for fuelwood in rural areas and the benefits
of biogas technology to drastically reduce time for fuelwood collection.
A study by Smith et al. (2013) at Okhombe community, a typical rural community
to the rural Maila, quantified the total benefits of the value of time, wherein the users
of biodigester at household level require the users to spend time feeding the system,
but it also considerably reduces the need for rural people to collect wood and saves
time. The total time saving due to cooking with biogas is a combination of time
saved on wood activities, cooking with traditional solid fuels, and cleaning cooking
utensils (Smith et al. 2013). Considering the total workload of women, biogas as a
new technology does not affect traditional working patterns. Cooking with solid
fuels on open fires or with traditional stoves results in high levels of air pollution
exposure due to pollutants such as small particles and carbon monoxide, and this
affects the health of users.
Many health benefits can result from moving from traditional energy sources to
cleaner fuels. According to the World Health Organization (WHO), over three billion
people worldwide continue to use solid fuels, including wood, dung, agricultural
residues, and coal, to supply their energy needs (WHO 2011). Indoor air pollution, a
significant proportion generated from traditional cooking stoves, is thought to be
responsible for 2.7% of the total global burden of disease (WHO 2011).
It was assumed that only households that cooked with solid fuels would benefit
from a reduction in indoor air pollution (IAP), and thus the calculation of IAP-related
deaths was based on the number of households that used fuelwood, cow dung, or
coal as their primary and/or secondary cooking fuel. It was assumed that the use of
biogas will reduce by 65% the IAP, and consequently IAP-related deaths will be
reduced by the use of biogas in place of traditional solid fuels.
The benefit of a biodigester (and the output of bio-slurry) to farming practice
was quantified as the avoided cost of purchased fertilizers. A well-designed
biodigester system, with the inclusion of rainwater harvesting systems and fodder
cultivation, has the ability to provide benefits well beyond the mere replacement of
purchased fertilizers.
A project in which biodigester household members are trained to use harvested
water and bio-slurry to grow food and fodder for their cattle has significant potential
to improve the health of both cattle and people as well as instigating improved cattle
management practice which will, in turn, contribute to the preservation of natural
resources. Further study on this topic is required, but it is believed that a suitable
fodder feeding program will benefit the health of cattle greatly and reduce grazing
pressures on the land – resulting in reduced erosion. These outcomes have great
potential in terms of food supply and resource management for sustainable devel-
opment. The increased economic benefit inherent in these outcomes is likely to
further increase the societal desirability of the technology.
The bio-slurry from the digesters at Maila cooperative is used to water the feeds
for cattle. Two types of grasses are being grown at the site, and they are watered by
the bio-slurry which is applied in order to demonstrate the usefulness’ of the
bio-slurry to replace the fertilizers.
Evidence from the monitoring process and expression by the biogas users at the
cooperative for cooking suggest that biogas if used to its full capacity can provide
enormous benefits. The cooperative members revealed that their lives have dramati-
cally changed ever since the introduction of the biogas digesters. They also have
reported that their monthly expenses on cooking energy sources have been reduced
dramatically since they no longer have to depend on fuelwood and LPG but rather
biogas. In addition to saving on fuelwood purchases, they identified that they no
longer needed to constantly manage cooking fires and that they were saving time as
they were simply able to turn the gas on, light it, and begin cooking without the need to
watch over the process. Timesaving, as a result of more efficient cooking practices and
reduced fuelwood purchases and collection, reveals that a biodigester could contribute
to promoting gender equality and empowerment of women as women are relieved of
time-consuming domestic duties, while efficient cooking fuel and reduced wood
harvesting also have the potential to ensure environmental sustainability.
Biogas technology provides social and economic benefits. It can improve the
health of users, is a sustainable source of energy, benefits the environment, and
provides a way to treat and reuse various wastes – human, animal, agricultural, and
municipal. The findings of the research strongly point out the significance of biogas
technology in this time to achieve energy sustainability and to solve the problem
of indoor air pollution in rural household, and to reduce the household energy cost
spent on energy sources for cooking and heating thus achieving the 2030 UN
Sustainable Development Goals.
Conclusions
In conclusion, the use of biogas technology as a clean and renewable energy to solve
the escalating energy problems in rural areas has been demonstrated in the rural area
wherein many benefits where experienced. However, there are alternatives to the use
of traditional biomass such as biogas technology, which can provide clean and
reliable energy services. The result is a better quality of life socioeconomically,
better health, and improved academic performance by children being able to study
for longer hours.
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A Review on Treatment of
Pharmaceuticals and Personal 59
Care Products (PPCPs) in Water
and Wastewater
Mukesh Goel and Ashutosh Das
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1434
Pharmaceuticals and Personal Care Products (PPCPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1434
Toxicity and Evaluation of Risks Associated to PPCPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1435
Treatment of PPCPs Present in the Water and Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1436
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1440
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1441
Abstract
Water is the central element of all vital social and economic processes. Because of
the development of consumer society, harmful chemicals are being generated in
huge quantities throughout the world. The problems derived from the toxicological
effects of these organic compounds must be resolved for the benefits of the entire
society. The problem is certainly complex, and it is imperative that novel procedures
are required to deal with this extensive range of tribulations. Though there are plenty
of water treatment methods, a significant number of chemicals are still present in
“clean” water. These chemicals are referred to as emerging contaminants (ECs).
Some emerging contaminants have been used for a long time but have only
recently been discovered in lakes, rivers, and groundwater – our drinking water
sources. Emerging contaminants are of many types and have many sources. One
large group consists of the pharmaceuticals and personal care products (PPCPs) that
we purchase and use regularly. Other categories include certain pesticides, nano-
materials, flame retardants, and plasticizers. Major sources of these chemicals
include residential, agricultural, and industrial activities. This chapter reviews the
various treatment technologies presently available for PPCP removal.
M. Goel (*) · A. Das

Centre for Environmental Engg., PRIST Deemed University, Thanjavur, Tamil Nadu, India

https://doi.org/10.1007/978-3-319-73645-7_41
1434 M. Goel and A. Das
Keywords
Emerging contaminant (ECs) · Pharmaceuticals and personal care products
(PPCPs) · Treatment · Water · Wastewater
Introduction
Water is the central element of all vital social and economic processes. Because of
the development of consumer society, harmful chemicals are being generated in
huge quantities throughout the world. The problems derived from the toxicological
effects of these organic compounds must be resolved for the benefits of entire
society. The problem is certainly complex, and it is imperative that novel procedures
are required to deal with this extensive range of tribulations. Though there are plenty
of water treatment methods, a significant number of chemicals are still present in
“clean” water. These chemicals are referred to as emerging contaminants (ECs)
(Barcelo and Petrovic 2007; Kumerer 2009; Kyle and Murray 2010).
Some emerging contaminants have been used for a long time but have only
recently been discovered in lakes, rivers, and groundwater – our drinking water
sources. In the last decades, rapid progress in detection methods has made it
conceivable to measure even a small concentration of ECs. Drinking water samples
in various places have reported the presence of these contaminants (Parrot and
Bennie 2009). Emerging contaminants are of many types and have many sources.
One large group consists of the pharmaceuticals and personal care products (PPCPs)
that we purchase and use regularly. Other categories include certain pesticides,
nanomaterials, flame retardants, and plasticizers. Major sources of these chemicals
include residential, agricultural, and industrial activities (Parrot and Bennie 2009;
Phillips et al. 2010). Primarily, they also enter through wastewater treatment plants.
These are hospital wastes, unaffected by conventional treatment processes.
Pharmaceuticals and Personal Care Products (PPCPs)
The greatest danger from the presence of pharmaceuticals in the water is not so much
the single type of pharmaceuticals, but it is when different chemicals are consumed
together and produce a magnified effect which is known as synergism. On top of this,
scientists are not aware of the effects of these combined pharmaceuticals.
PPCPs include prescription and non-prescription medications, nutritional supple-
ments, diagnostic agents, as well as other consumer products such as disinfectants,
fragrances, sunscreen, and cosmetics. Even though most of them are polar, have a
short half-lifetime in water, and are found in trace concentrations, they are consid-
ered pseudo-persistent pollutants. This is because their universal, frequent usage by
multitude of individual and animals causes a continuous discharge into the environ-
ment oftentimes sourcing from either untreated or insufficient wastewater treatment.
59 A Review on Treatment of Pharmaceuticals and Personal Care Products (PPCPs). . . 1435
Some PPCPs are easily broken down and processed by the human body or
degraded quickly in the environment, but others are not easily broken down and
processed, so they enter domestic sewers. Because they dissolve easily and do not
evaporate at normal temperatures or pressure, PPCPs make their way into the soil
and into aquatic environments via sewage, treated sewage sludge (biosolids), and
irrigation with reclaimed water (Xu and Wu 2009; Zhou et al. 2009). An important
source of PPCPs in groundwater is from municipal landfills through leachate.
There are thousands of chemicals that are constituents of PPCPs. These are
diverse and are used as active ingredients or preservatives in cosmetics, skin care,
dental care, hair care products, soaps, cleansers, insect repellents, sunscreen agents,
fragrances, and flame retardants. Pharmaceuticals and personal care products were
first called “PPCPs” only a few years ago, but these bioactive chemicals (substances
that have an effect on living tissue) have been around for decades. Their effect on the
environment is now recognized as an important area of research (Lindberg et al.
2007; Scheurer et al. 2011).
Toxicity and Evaluation of Risks Associated to PPCPs
The toxicological problems posed by these PPCPs have created a great concern
among scientists. Several studies are being conducted to ascertain the incumbent
damage in relation to existence of PPCPs and other emerging organic contaminants
on aquatic organisms and other components of the ecosystem. Though their con-
centrations are very low (ng/L to μg/L) and may not cause an immediate risk to
human health, their presence seems to create an environment of anxiety. It is still
debatable whether they are actually harming the environment or not, in the present
intake. Most probably, the recycle and accumulation in the wastewater in time to
come will become serious environmental issues. It has been observed that aquatic
organisms such as fish would be exposed to PPCPs during the course of their life
cycle. The contact of fish with these chemicals resulted in changes in sperm density,
gonad size, male sex reversal, and other health issues (Kolpin et al. 2002).
Similarly, Brain et al. (2004) reported the effect of atorvastatin, a lipid regulator
on aquatic macrophytes at 26 ppb. The synthetic hormone 17-ethinylestradiol has
been shown to cause feminizing effects in fish at very low concentrations (Parrott
and Blunt 2005). The transformation products of PPCPs have not been explored
adequately, though there are a few reports. Gomez et al. (2012) noted transforma-
tion products of PPCPs at the Henares river basin in Spain at a very high
concentration. Interestingly the concentration of these intermediates was higher
than those of parent compound discharged from wastewater treatment plant.
Likewise, Quintana et al. (2005) reported several alteration products of ibuprofen
and other pharmaceuticals. There are some alarming incidents such as reduction of
the population of vultures in India and Pakistan due to the use of diclofenac on
cattle in these countries. There are many other dangerous omens found all over the
world (Ong et al. 2009).
Treatment of PPCPs Present in the Water and Wastewater
The methods that are normally employed to treat the water are aimed at removing
and reducing overall groups of contaminants to a safe level. However, PPCP
treatments are not encouraging, as even the so-called clean water seems to have
appreciable concentration of these chemicals. Thus, it is important to develop
effective technologies to remove these compounds from drinking water.
Various treatment methods presently used for removing PPCPs are described
below:
Advanced oxidation processes (AOPs): Conventional oxidation processes use
oxidants like Cl2 ozone (O3), H2O2, and so on. Some of the oxidants are common in
drinking water treatment, but they suffer from various disadvantages, such as
production of trihalomethanes (THMs), haloacetic acids (HAAs), and other harmful
by-products. The advanced oxidation processes (AOPs) generate free radicals,
which act as strong oxidant to destroy the organic pollutants. AOPs are defined as
the process which entails the generation of highly reactive radicals (especially
hydroxyl radicals) in ample quantity to affect water purification. Rate constants are
usually in the range of 108–1011 L.mol1 s1. Hydroxyl radicals (OH) react with
almost all organics and are stable over a wide range of pH, which makes them highly
attractive for wastewater treatment. AOP includes several methods such as H2O2/UV,
O3/UV, and UV/TiO2. Being a destructive technology, it has significant benefits for the
wastewater treatment. AOPs have the distinction of being stand-alone, or it can also be
joined with other physicochemical or biological processes. Process coupling is
conceptually beneficial usually leading to improved treatment efficiencies (Renugoat
et al. 2012; Mohapotra et al. 2013). Advanced oxidation techniques like ultra-
sonication (Nie et al. 2014), advanced Fenton, UV/H2O2 (Deng et al. 2013), advanced
photocatalytic oxidation (Bae et al. 2013), and TiO2 photocatalytic ozonation
(Márquez et al. 2014) have been reported.
Advantage of AOPs can be summed up as follows:
• It does not transfer the pollutants from one phase to another. It completely
mineralizes them.
• Operation is done at mild conditions of temperature and pressure.
• Reaction rate is very high.
However, it has certain disadvantages, primary among them are:
• Lack of sound knowledge of process design and operation of large-scale reactors.

• These processes are comparatively costly. The cost includes the cost of equipment
and the intense energy required to run the process.
Coagulation–flocculation: Coagulation is used for removing particulate mat-

ter, colloids, as well as some dissolved substances. Coagulation–flocculation
processes have so far yielded ineffective elimination of most micropollutants.
Matamoros and Salvadó (2013) reported the treatment of micropollutant in

a coagulation–flocculation chamber for treating secondary effluent. Fifty
percent removal was observed for galaxolide, tonalide, and octylphenol. Suárez
et al. (2009) reported significant reduction (around 80%) of musks during
coagulation–flocculation treatment of hospital wastewater. Carbella et al. (2010)
conducted lab-based experiments to observe the effect of coagulant loading,
coagulant identity, time of mixing, and temperature on PPCP degradation. Only
20% removal was observed.
Ozonation: Ozonation, though part of AOPs, stands out because of its versatile use
in wastewater treatments. Ozone has been used for removing micropollutant load of
full-scale WWTPs (Synder et al. 2006). Similarly Zimmemann et al. (2011) examined
the efficacy of ozonation for removing micropollutants. The removal was on higher
side. Studies have shown that ozone can reduce the concentrations of many PPCPs in
wastewater (Lee et al. 2012; Rosal et al. 2010). Ozonation of PPCPs resulted in
complete degradation of macrolides, estrogens, and sulfonamides. Oher chemicals,
such as diclofenac and naproxen, were also transformed (Huber et al. 2005). Removal
of sulfonamides using ozone is extensively studied by Garoma et al. (2010). Sulfon-
amides are highly used in the USA and can be excreted by the body at high rates. They
tested the sulfonamide degradation for varying pH, ozone concentration, and bicar-
bonate ion concentration. Higher pH and higher ozone concentration facilitated the
faster degradation of sulfonamides and intermediates. Similarly Von Gunten (2003)
observed the effect of nitrite and ammonia on ozonation of EE2 (17α-ethinylestradiol).
Bromate formation through ozonation of bromide-containing waters is one of the
shortcomings in ozonation. Bromate is a potential hazard. Similarly, Andreozzi et al.
(2001) report ozonation of carbamazepine (CBZ), an antiepileptic drug. Nitrite and
nitrate positively affected the ozonation of CBZ and increased the speed of CBZ
transformation. On the other hand, humic acid was detrimental in CBZ degradation
and reduced the efficacy of the process. Once again, the expensive ozone and its lack of
application in treatment plants handicap versatile ozonation.
Photocatalysis: Heterogeneous photocatalysis with titanium dioxide is reported
to be effective and useful for the management of non-biodegradable wastewaters
containing recalcitrant compounds (Gouvea et al. 2000; Yeber et al. 2000). Hetero-
geneous photocatalysis can take place in all the fluid media such as gas phase, pure
organic liquid phases, or aqueous solutions. The classical heterogeneous catalysis
comprises five steps. Frist step is the transfer of reactants from fluid phase, which is
followed by adsorption of a minimum of one reactants, and then reaction in the
adsorbed phase. The reaction is succeeded by desorption of the product and finally
removal of the products from the interfacial region (Herrmann 1999).
The photocatalytic reaction takes place in the adsorbed phase. It is similar to
typical catalysis process, difference being photonic activation replaces the thermal
activation of catalyst. The adsorption of photons results from the illumination of
semiconductor catalyst with photons, provided energy of photons is larger than the
conductors’ bandgap energy. This process leads to the formation of electron-hole
pairs, which further divides into free photoelectrons in the conduction band and
holes in the valence band.
The hole can either oxidize a compound directly or react with electron donors like
water to form OH radicals, which in turn react with pollutants such as chlorophenols
and dyes. TiO2 is generally preferred as the catalyst because of its stability, good
performance, and low cost (Andreozzi et al. 2000). The disadvantage is of the
catalyst separation from solution, as well as the fouling of the catalyst by the organic
matter. Apart from TiO2, various oxides and sulfides have been used as catalysts:
ZnO, CeO2, CdS, ZnS, etc. (Herrmann 1999).
The following reactions take place during the photocatalytic degradation of
organics using TiO2:
TiO2 þ hv ! e þ hþ (1)
O 2 þ e ! O
2 (2)
H2 O ! OH þ Hþ (3)
OH þ hþ ! OH • (4)
O þ
2 þ H ! HOO • (5)
2HOO • ! O2 þ H2 O2 (6)
H2 O2 ! 2OH • (7)
R H þ • OH ! R • þ H2 O (8)
R • þ • OH ! R OH (9)
R OH þ • OH ! Intermediates ! CO2 (10)
Heterogeneous photocatalysis has been studied in detail. PPCP degradation can

take place by direct photolysis (Klavarioti et al. 2009). Gomes et al. (2017) reported
the photocatalytic ozonation of paraben using TiO2 doped with noble metals such as
Ag, Au, Pt, and Pd. They observed that combining photocatalysis with ozone led to
reduced usage of ozone thus making the process economical and more feasible. 0.5%
Ag-TiO2 was found to be the best catalyst resulting in total paraben removal.
However, it was also noted that toxic by-products generated from photocatalytic
ozonation of paraben were not completely mineralized.
Constructed wetland: Constructed wetland (CWs) is a wastewater treatment
system that has the potential of reducing pollutants to levels that will meet existing
standards for water quality before discharging to the environment. CWs are probable
contenders to remove different kinds of pollutants such as organics, suspended
solids, pathogens, nutrients, and heavy metals from wastewater (Antoniasdis et al.
2007). There are two basic kinds of constructed wetlands, horizontal flow (HF) and
vertical flow (VF). CW was found to be effective for reservoir effluent, and removal
efficiencies were reported to be 90.4% for TSS and 62.4% for COD (Avsar et al.
2007). Huett et al. (2005) described the application of HF-constructed wetland for
nitrogen and phosphorus removal. They found more than 96% removal with Phrag-
mites australis, but unplanted wetlands were unproductive and produced only 16%
nitrogen removal. Calheiros et al. (2007) reported similar results. They accomplished
effluents with nitrogen concentration of less than 1 ppm and phosphorous with
0.05 ppm. Aslam et al. (2007) studied the performance of VF-constructed wetland
for the treatment of refinery wastewater. They used Phragmites karka and were
successful in the reduction of TSS, COD, and BOD. They also compared the
compost- and gravel-based wetland and observed the superior performance of
compost-filled wetland.
Matamoros et al. (2005) reported the removal of ibuprofen (IB) using HF and
VF. Matamoros et al. (2007) found a prevalence of OH-IB over Ca-IB metabolite in
a HF wetland, which would be explained by its predominant aerobic biodegradation.
A study by Heberer (2002) showed that persistent chemical like diclofenac was
successfully degraded using constructed wetlands. Matamoros and Bayona (2006)
stated lower removal of diclofenac, while Avila et al. (2010) observed approximately
99% degradation using HF. IB was also successfully tested by Hijosa-Valsero et al.
(2011), where they observed lower degradation in winter but more than 90%
removal in summer season. There are also reports on the removal of ethynilestradiol,
musk fragrance and tonalide, triclosan, etc. using constructed wetland (Park et al.
2009; Matamoros et al. 2007). Song et al. (2009) did a comparative study on
saturated and unsaturated VF for ethynilestradiol degradation and observed that
unsaturated VF produced high efficiency of removal.
Membrane filtration: Membrane technology, particularly nanofiltration
(NF) and reverse osmosis (RO), is another option for augmenting PPCP removal
from wastewaters. The choice of an appropriate membrane process depends on the
scope of removed effluents and admixtures present in water. They can be used to
remove effluents as independent processes or be combined with unit complemen-
tary processes, forming a treatment process line. Increasingly, NF/RO membranes
have been successfully applied in removing micropollutants from the aquatic
environment (Yang et al. 2011; Serrano et al. 2011; Sahar et al. 2011; Chon
et al. 2012).
Adsorption: In the last decades, several studies were carried out to remove
emerging pollutants by adsorption process. Commercial adsorbents such as natural
clays, minerals, and activated carbons have been used (Yoon et al. 2005; Snyder
et al. 2007). Redding et al. reported the treatment of a lake water spiked with
29 EDCs and PPCPs with concentration values of 100–200 ng/L. There are other
successful studies by Sotelo et al. (2012). Modified adsorbents have also been
successfully employed in the treatment of PPCPs containing water. Zhuo et al.
(2017) described the adsorption of PPCPs (benzoic acid (BEN), ibuprofen (IBU),
and ketoprofen (KET)) onto the two composite beads of porous metal–organic
frameworks (MOFs) containing chitosan and sodium alginate. It was observed that
MOFs containing chitosan reported higher adsorption capacity. There are other
reports enumerating the adsorption capacity of chitosan, especially nano chitosan.
It has drawn particular attention as effective nanosorbent due to its low cost and its
high contents of amino and hydroxyl functional groups showing high adsorption
potential for various aquatic pollutants (Crini and Badot 2008; Chatterjee et al.
2009; Guibal et al. 2006). Apart from that, there is another category of adsorbents,
magnetic nanoparticles, which are reported to have high affinity toward organics.
Besides, these can be easily separated from the process stream owing to their
magnetic nature (Nassar 2010; Ruzmanova et al. 2013; Ochando-Pulido et al.
2013). Magnetic resins were also found to be effective adsorbents for water
treatment and PPCP removal (Zhu et al. 2016). They compared the adsorption
behavior of this resin with two activated carbons, namely, Norit and F400D.
Norit was faster in removing PPCPs compared to magnetic resin. However,
humic acid could not affect the adsorption performance of resin, while both the
activated carbons were affected. Besides, resin displayed enhanced regeneration
potential.
Conclusions
We are living in the world of water crisis, thanks to our unchecked industrial
pollution and population explosion leading to massive diversification of freshwater
for agriculture and urban needs. Moreover, global climate change variation, which
has resulted in repeated tragedies in India, will certainly impact water issues. The dry
regions of North Africa, Asia, Europe, etc. have to deal with water shortages in the
coming decades. The industrialized countries like the USA have its own issues with
the water, thanks to massive consumption in the industry as well as in domestic
sector. The USA has faced the most severe drought in the last decades. Similarly,
China is confronted with the fact that their biggest rivers are exorbitantly polluted,
which cannot be even used for irrigation.
All these countries now have to deal with additional sets of problems unheard of
in the last decades. The policy makers in several countries are in great anxiety and
are devising various strategies to treat these malign chemicals. The search for water
treatment, however, should not lead to uneconomical and impractical solutions
causing more problems in the future. This chapter presented a detailed review on
PPCP removal from water and wastewater. Novel technologies are required to deal
with this menace, conventional technologies will fail, and they can produce more
harmful by-products. Nanocomposites are likely nano-adsorbents that can remove
PPCPs from waters. They have diversified applications in different areas such as
biological sciences, drug delivery systems, and wastewater treatment. Modified
nanocomposites such as magnetic nanocomposites are much more efficient class
of nanocomposites in which magnetic nanoparticles are dispersed in a magnetic or
nonmagnetic insulating matrix. The shape, size, and distribution of the magnetic
particles play an important role in determining the properties of such materials.
Magnetic nanocomposites are proved to be better than nanocomposites as they have
the advantages of both magnetic separation techniques and nano-sized materials,
which can be easily recovered or manipulated with an external magnetic field. They
are also very effective for the removal of both organic and inorganic pollutants from
the pollutant water.
Cross-References
▶ Advancement of photocatalytic water treatment technology for environmental

control
▶ Biostimulation and Bioaugmentation: An alternative Strategy for Bioremediation
of ground water contaminated mixed landfill leachate and sea water in low income
ASEAN countries
▶ Biotechnological Approach for Mitigation Studies of Effluents of Automobile
Industries
Constraints
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Constructed Wetland: A Green Approach
to Handle Wastewater 60
Ashutosh Das and Mukesh Goel
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1446
Types of Constructed Wetlands and Their Suitability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1446
Types of Wetland Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1447
Transformation Mechanisms of Major Nutrients and Metals in Wetlands . . . . . . . . . . . . . . . . . . . . 1449
Nitrogen Transformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1449
Phosphorus Cycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1450
Nutrient Uptake by Wetland Vegetation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1451
Sulfur Cycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1451
Pathogen Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1451
Water Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1452
Standard Wetland Systems for Treatment of Specific Wastewater Types . . . . . . . . . . . . . . . . . . . . . 1452
Dairy Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1454
Landfill Leachate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1454
Oil and Grease-Rich Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1455
Pulp and Paper Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1455
Acid Mine Drainage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1456
Winery Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1456
Limitations of Wetland Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1457
Operation and Maintenance of Constructed Wetlands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1457
Operation and Maintenance of FWS Wetlands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1458
Operation and Maintenance of VSB Wetlands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1460
Cost of Wetland Treatment Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1462
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1462
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1463
A. Das · M. Goel (*)

Centre for Environmental Engg., PRIST Deemed University, Thanjavur, Tamil Nadu, India

https://doi.org/10.1007/978-3-319-73645-7_42
1446 A. Das and M. Goel
Abstract
Natural wetlands are able to manage all local contamination by naturally occurring
agents such as sunlight, aeration, biotic interaction, microbial action, precipitation,
and gravitational attraction. Contaminants are removed from the system through
volatilization, sedimentation, infiltration, dilution, and oxidation, among others.
Constructed wetlands aim to simulate a natural wetland system through optimal
configurations of wetland plant types and density, waste characteristics, flow rate,
soil types, and stratification. In this way, wastewater can be effectively treated in a
natural way, without heavy machinery and additional chemicals that may increase
pollution. This chapter discusses the different types of constructed wetlands, the
types of wetland plants, and the transformation mechanisms of major nutrients and
metals in wetlands, along with suitability and limitations. Finally, the operational
requirements, maintenance, and cost of a wetland system are described.
Keywords
Constructed wetland · Free water surface (FWS) · Vegetated submerged bed
(VSB) · Nutrient transformation
Introduction
Although natural wetlands have always been used as sinks for wastewater,
engineered wetland systems were only conceptualized in the past century to simulate
a natural wetland’s characteristics (Wallace and Robert 2006). Phenomenal growth
in constructed wetland technology has occurred all over the world especially,
because of their ability to recycle, transfer, and immobilize a wide range of potential
contaminants (Vymazal 2005, 2010; Greenway 2007; Kadlec and Wallace 2009). In
fact, constructed wetlands are especially suitable for small communities in develop-
ing countries due to their adaptability to locally available materials, lack of depen-
dency on electric power, lack of requirements for skilled manpower in operation and
maintenance, and non-dependency on centralized waste-treatment facilities (Denny
1997; Cooper and Findlater 2013).
Types of Constructed Wetlands and Their Suitability
Three constructed wetland systems are discussed in the literature: hydrobotanical

systems (Pawęska and Kuczewski 2013), aquaculture systems (Brix 1999), and soil
systems (Blazejewski and Murat-Blazejewska 1997). Of these, soil systems are most
studied because of their abundance and simplicity (Cooper and Findlater 2013).
Small-scale constructed wetlands essentially comprise four types: free water surface
(FWS), vegetated submerged bed (VSB), vertical flow (VF), and sludge dewatering
reed bed (SDR) (Wallace and Robert 2006).
FWS wetlands have areas of open water, floating vegetation, and emergent
vegetation, thus providing a habitat for a variety of wildlife, similar to natural
60 Constructed Wetland: A Green Approach to Handle Wastewater 1447
wetlands (Knight 1993; Kadlec and Knight 1996). These wetlands are most suited to
warmer climates because of their higher biological decomposition rates. FWS
wetlands are generally used for treating effluent from secondary treatment processes
(e.g., trickling filters, oxidation ponds/lagoons, activated sludge units) rather than
directly as a secondary treatment process because of the potential for human
exposure to pathogens. Based on soil conditions, berms, dikes, and liners may be
used to control flow and infiltration in such wetlands. Essentially, basic wetland
treatment includes the processes of sedimentation, filtration, oxidation, reduction,
adsorption, and precipitation (U.S. EPA 2000).
In VSB wetlands (also known as subsurface-flow wetlands), the wastewater stays
below the ground’s surface. Thus, unlike in an FWS wetland, the risk of human
exposure to pathogens is minimal, as is the breeding of mosquitoes and other vector
organisms. Generally, VSB wetlands consist of a lined gravel or soil-based bed that
is planted with emergent vegetation. The wastewater is treated as it travels through
the gravel media and root zones (especially rhizomes). VSB wetlands are low-cost
and low-maintenance systems; they are most suitable for single-family homes or
small cluster systems.
VF wetlands, as the name indicates, allow effluents to be filtered vertically,
similar to sand filters. Wastewater travels across the surface of a sand or gravel
bed (which is planted with wetland vegetation) through the plant root zone. This
process yields nitrified effluent through the oxidation of ammonia—something that
is not possible in VSB wetlands. These systems are used in combination with VSB
wetlands in many European countries, resulting in a nitrification-denitrification
treatment process (Cooper et al. 1999).
SDRs (reed beds) were developed by Seidel in the early 1960s. This system is
essentially an enclosed basin with a sand layer underlain by drainage pipes. The
evapotranspiration capacity of emergent wetland plants (typically Phragmites) dewa-
ter sewage sludge. These wetlands are less common than the other three types.
Types of Wetland Plants
All wetlands depend on plants to shade the water column, act as substratum for
biofilm growth, and cycle nutrients and organic carbon. However, FWS wetlands are
more dependent on plants than are VSB wetlands. Although several species of plants
can be sustained in wetlands, only a few species are widely used because of their
tolerance to high nutrient levels, saturated soil, and anaerobic conditions, as well as
their ability to propagate through rhizome spread and their local availability (Wallace
and Robert 2006).
When selecting plant types for a wetland system, the following parameters should
be evaluated:
• Hydrology: The water level at peak and normal flow can be used to determine
variability in thickness, frequency and duration of an unsaturated environment,
and inundation.
• Climate and latitude: It is preferable to choose plant types that are able to survive
in the local climate.
• Cost and availability of plant stock: It is preferable to choose native species rather
than exotic species.
• Plant size: A larger root biomass is preferable for a higher rate of survival and
prevention of weeds.
• Rate of colonization: The spreading rate of the plant species dictates the require-
ments for the initial planting stock. Balanced spreading is desired; fast spreading
reduces weed invasion, whereas slow spreading reduces species diversity.
• Water quality: In particular, variations in salinity, pH, alkalinity, and oxygen
demand should be within the tolerance levels of selected plants.
• Objectives: A wildlife habitat would require a predetermined threshold diversity
level, whereas wastewater treatment is better accomplished by a simple planting
scheme with less diversity.
• Maintenance: Especially during the first year, maintenance should include remov-
ing invasive vegetation, maintaining water levels, removing plant detritus
deposits, ensuring good oxygen transfer, and preventing mosquitoes (Wallace
and Robert 2006).
For FWS Wetlands (Fig. 1), emergent wetland plants are preferred. Sedimentation
can be increased by reducing wind-induced mixing and resuspension, The additional
surface area can increase biofilm growth and the uptake of soluble pollutants for a
range of treatment mechanisms. Particle interception is also increased. Shade is
provided from the plant canopy over the water column, thus reducing algae growth.
Fig. 1 Schematic of FSW and VSB wetlands

Furthermore, flocculation of smaller colloidal particles into larger, settleable parti-

cles is induced (Sinclair Knight Merz 2000). Ideal plants include perennial and fast-
growing species with high lignin content to provide a year-round aboveground
structure, including cattails (Typha spp.), bulrushes (Scirpus spp.), and common
reeds (Phragmitesaustralis).
VSB wetlands (Fig. 1) are less dependent on plants. However, they still require
careful planting, preferably with plants that have significant root penetration into the
bed media. This provides more surface area for biofilm growth, chemical exudates
that detoxify the root environment, and the introduction of fungi species and
symbiotic bacteria. Studies on VSB wetlands have not provided significant evidence
on the relationship between plant types and treatments (Gersberg et al. 1984;
DeBusk et al. 1989; Van Oostrom and Cooper 1990; Batchelor et al. 1990; Knight
1993). However, plants that are easy to propagate and are able to survive in relatively
hostile environments are suitable for a VSB wetland, including mostly Phragmites
(common reed) and Phalarisarundinacea (reed canary grass; Vymazal 1998).
Plant selection for VF wetlands and sludge dewatering beds (reed beds) have not
been explored much in the literature because they are used less often than FWS and
VSB wetlands.
Wildlife grazing may need to be considered for the protection of wetland plants.
Whitetail deer (Odocoileusvirginianus), for example, threaten winter plantation in
VSB wetlands in North America, which is often countered by spring plantation.
Similarly, Canadian geese (Brantacanadensis) can affect FWS wetlands by obliter-
ating the planting stocks. Proactive methods of animal control (e.g., screening,
deterrents) are often employed to deal with these situations.
Transformation Mechanisms of Major Nutrients and Metals

in Wetlands
The migration and transformation of nutrients and metals in a wetland are affected by
a wide range of factors, including settling (or vertical stratification), dispersion,
preferential flow, loading characteristics (hydraulic and organic), and basic hydro-
logical variants such as precipitation, evapotranspiration, infiltration, runoff, and the
overall water balance. The most common transformation phenomena are discussed
in this section (Wallace and Robert 2006).
Nitrogen Transformations
The redox conditions in wetlands are affected by oxygen transfer and organic matter
loadings (both internal and external). Nitrogen can exist in various forms in wet-
lands, such as ammonia, nitrite, nitrate, organic, and gaseous nitrogen.
Mineralization (also known as ammonification) is the process of converting
organic nitrogen into inorganic nitrogen (especially ammonia) in either aerobic or
anaerobic conditions; the process occurs the quickest in oxygenated zones. Most of
the nitrogen present in domestic wastewater ends up as organic nitrogen or ammonia.

The mineralization rate in wetlands depends on the temperature (doubling with a
temperature increase of 10 C), pH (optimum pH is between 6.5 and 8.5), carbon-to-
nitrogen ratio of the residue, available nutrients in the system, and characteristics of
the wetland substrate (namely, texture and structure) (Reddy and Patrick 1984;
Reddy et al. 1979).
Ammonia volatilization involves ammonium-nitrogen (equilibrated between gas-
eous NH4+ and aqueous NH3) escaping from soils and sediments in wetlands; the
levels are significantly higher when the pH is greater than 8.0 (Reddy and Patrick
1984). The most conducive environments for this process are submerged vegetation
and algal photosynthesis (through depletion of carbon dioxide and bicarbonate ions
from the water column). Ammonia volatilization is affected by the NH4+ concen-
tration in water, temperature, wind velocity, solar radiation, type and number of
aquatic plants present in the system, and the capacity of the system to change the pH
during diurnal cycles (Wetzel 2001; DeBusk et al. 2004; Vymazal 1995).
Nitrogen reduction (denitrification) refers to the reduction of oxidized nitrogen
compounds (nitrate or nitrite) to nitrogen gases (N2 and N2O), which vent from the
water column. This phenomenon is caused by a variety of bacteria and some fungi
under both aerobic and anaerobic conditions. Denitrification is able to proceed soon
after the onset of anoxic conditions (a redox potential of approximately 220 mV)
(Hauck 1984). The denitrification rate depends on the biochemical oxygen demand
(BOD) of wastewater (which is the carbon source required for the process), temper-
ature, type of available carbon, and carbon-to-nitrogen ratio in the system (Ingersoll
and Baker 1998; Baker 1998; Hume et al. 2002a,b).
Nitrogen transformation in FWS wetlands is essentially guided by the amount of
dissolved oxygen available in the wetland system, where the decay of plant detritus
often serves as the main source of this organic carbon. The relative magnitude of
these mechanisms changes both daily and seasonally (Liehr et al. 2000; Gerke et al.
2001; Shipin et al. 2004). Here, in the root rhizosphere, bacteria compete for organic
oxidation, nitrogenous complexes, and sulfides. Most VSB wetlands are primarily
used for treatment of high BOD and anaerobic effluents. Thus, mineralization that
leads to the formation of ammonia occurs here more often than in FWS wetlands due
to their lower oxygen availability. Hence, the influent pH of the water and the bed
media is the factor affecting nitrogen transformation (Johns et al. 1998).
Phosphorus Cycling
Because of the high phosphorus and nitrogen loadings in wastewater, constructed

wetlands are often significantly richer in nutrients than are natural wetlands. In FWS
wetlands, phosphorus is mostly cycled sequentially: net plant uptake, sorption, and
sedimentation/degradation (accretion through direct settling and trapping) of plant
biomass through growth, death, and decay (Kadlec and Knight 1996; Craft and
Richardson 1993; Kadlec 1994). The rate of phosphorus removal is determined
primarily by the phosphorus loading rate, size of the wetland, prevailing climatic
conditions, and type of vegetation (Vymazal 2001; Kadlec 1999). In VSB wetlands,
the plant components quickly reach an equilibrium with the influent phosphorus,
leading to poor removal of phosphorous unless special bed media are used.
Nutrient Uptake by Wetland Vegetation
The available nutrient content in the tissues of wetland plants and their growth rates
determine their nutrient uptake and storage potential, which is greater in constructed
wetlands than natural wetlands (Greenway 2003). Interestingly, most of the nutrients
incorporated into plant tissue during growth can return to the water column through
decomposition if the wetland is not harvested (Reddy and DeBusk 1987). The
amount of nitrogen and phosphorus that can be removed by harvesting is generally
insignificant compared to applied wastewater loads; it does not exceed 10% of the
total removed nutrients (both nitrogen and phosphorus), even in well-developed
constructed wetlands with emergent macrophytes (Brix 1994; Vymazal 2001;
Gersberg 1986; Herskowitz 1986; Vymazal et al. 1999).
Sulfur Cycling
Sulfate is probably the most common anion in surface waters. Its formation through
oxidation indicates aerobic conditions, whereas its reduction to sulfide indicates
anaerobic conditions (similar to ammonia). In VSB wetlands, sulfide oxidation to
sulfate occurs in parallel to and competes with nitrification, which is also associated
with heavy metal precipitation (especially copper and nickel) (Eger 1992; Eger and
Lapakko 1989; Frostman 1993).
Pathogen Reduction
The four common pathogens found in domestic wastewater are bacteria, viruses,
protozoa, and helminths, which often sustain the regular treatment train. Several
pathogens can be removed through wetland treatment, including fecal streptococci,
salmonellae, Yersinia, Pseudomonas, and Clostridium bacteria species, through
physical (e.g., filtration, ultraviolet disinfection, sedimentation), chemical (e.g.,
oxidation, wetland generated-biocidal disinfection, adsorption into organo-
sorbents), and biological (e.g., predation, natural death) pathways (Herskowitz
1986; Gersberg et al. 1989). In FWS wetlands, all of these pathogen removal
processes have been demonstrated with ultraviolet radiation exposure in proportion
to open-water areas (Mara 1976). In Fish & Wildlife Service (FWS) wetlands with
high populations of birds and warm-blooded animals, higher levels of certain
pathogen occur from these non-human sources, including fecal contamination,
streptococci, and salmonella (PBSJ 1989).
Although VSB wetlands also offer robust pathogen removal (more than 90%),
few studies have investigated the removal mechanisms. In these systems,
sedimentation, filtration, and interception seem to be common removal processes,

especially for helminth ova; adsorption and natural death are used for bacteria and
viruses (Gerba et al. 1999; Thurston et al. 2001; Gersberg et al. 1989; Mandi et al. 1998;
Stott et al. 2002). Pathogen removal efficiency has been reported to be higher when the
fineness of bed materials and retention time are increased (García et al. 2003a,b).
Water Temperature
Thermal energy gains (through solar radiation and influent water temperature)
and losses (through evapotranspiration and effluent flow temperature) are asso-
ciated with diurnal and seasonal cycles, which cause short- and long-term water
temperature variations, respectively. Additionally, ground-heat storage transfer
forms a two-way transfer mechanism, from the wetland to the ground during
summer (because of high solar radiation) and from ground to the wetland during
winter (because of low solar radiation). A similar two-way mechanism has also
been observed for convective energy transfer, wherein the wetland receives
energy from the air or releases heat energy back to air, depending on the
difference between the air temperature and water temperature.
When the energy inputs and outputs are balanced on seasonal basis, the water
temperature is said to be a balance point temperature, which is usually observed in
wetland-inlet zones. Depending on the degree of vegetative cover, climate, and solar
intensity, FWS wetlands typically show temperature variations on both daily and
seasonal bases, ranging from 5 C to 15 C (Kadlec and Knight 1996; Kadlec and
Reddy 2001). In VSB wetland systems, the temperature response of the wetland is
related to the air temperature in tropical and equatorial regions; in temperate regions,
leaf litter on the top of the system has been observed to play a role in retaining and
transferring heat (Kadlec and Knight 1996; Kadlec 2001a).
Standard Wetland Systems for Treatment of Specific Wastewater

Types
As discussed previously, two standard wetland systems are used extensively

around the world: free water surface and vegetated submerged bed wetland
systems. FWS wetlands are the earliest engineered wetland designs. VSB
constructed wetland systems were introduced more recently; hence, the technol-
ogy is continuing to develop. The main characteristics of these two wetland
systems are presented in Table 1.
Domestic and municipal wastewater can be efficiently treated by small-scale
constructed wetland systems. They also can treat several other types of wastewater,
either remedially or industrially. The following sections discuss some of the wetland
treatment systems used in a variety of special applications.
Table 1 Comparative analysis of free water surface and vegetated submerged bed wetland
systems
Salient features Free water surface (FWS) Vegetated submerged bed (VSB)
Structure of wetland Emergent wetland plants, open Gravel or soil-based beds are
water, and a lined/unlined basin. planted with wetland vegetation.
Soil forms the rooting media, Wastewater is not exposed
above which a water layer is during treatment because it is
maintained. This leads to kept within the bed media and
constant anaerobic soil hence not provide habitat for
conditions, with breeding of mosquitoes or other vector
mosquitoes and other vectors organisms
Influent wastewater Used for treated wastewater (not Most commonly used to treat
type usually raw domestic waste) to primary domestic wastewater to
avoid exposure to pathogens and secondary effluent discharge
vectors standards
Size and cost Suitable for large size with high Well suited for treating very
wastewater flow (more than small wastewater flows (less than
75,000 m3/d) with less chance 75 m3/d) and higher cost on
for hydraulic failure and lower per-hectare basis
cost on per-hectare basis
Effect of treatment Physical treatment involves Less understood with regard to
mechanisms (either gravitational settling, diffusion, physical and chemical treatment
simultaneously or and volatilization, leading to mechanisms and effects. In
sequentially) reduction of dissolved and relation to biological treatment,
particulate contaminants. VSB is better than FWP because
Chemical treatment involves of its significantly larger
absorption, ultraviolet radiation, available surface area for
and chemical precipitation, microbial growth, thus
leading to removal of improving efficiency of the
phosphorus and dissolved system. The increased microbial
metals. Biological treatment density allows for a much
involves transforming organic smaller system footprint
matter and nitrogenous compared to FWS systems
constituents. Here, submerged
plant shoots in addition to
suspended-growth systems such
as lagoons provide an increased
surface area for microbial growth
Use in cold climates Water temperature affects the Unlike FWS, the normal
rate at which biological accumulation of plant detritus
processes occur. Effluent water may not provide enough
temperature closely mimics air insulation to keep the system
temperature during non-ice from freezing. Hence, insulating
periods, whereas ice formation materials (e.g., hay, straw, wood,
limits functionality during icy mulch) are used for insulation
periods
Wildlife habitat and More suited Less suited
aesthetic appeal
Dairy Wastewater
Dairy wastewater is a mixture of two distinct wastewater types: wastewater from

cleaning and sterilization/pasteurization and wastewater from the washing of cow-
shed in various proportions at different dairies. Although FWS and VSB wetlands
have been used for the treatment of dairy wastewater, the former is less effective than
the latter wetland system because of insufficient oxygen transfer and hence anaero-
bic conditions (especially because of the high effluent concentration of ammonia
nitrogen) (Newman et al. 2000; Schaafsma et al. 2000). However, the milk proteins
in this wastewater degrade much slower than in domestic wastewaters, which needs
to be considered in the system design. Thus, designers should use this approach with
caution. Vertical-flow wetland processes with high rates of oxygen transfer have
been found to be successful in treating dairy wastewater (Green et al. 2002; Liénard
et al. 2002).
Landfill Leachate
The chemical characteristics, concentration, and volume of leachate depend on the

source waste material disposed of at a particular landfill site, its stage of decompo-
sition, the lining of landfill cells (or lack thereof), and the rate of groundwater flow
through the waste material. The basic decomposition of municipal solid waste occurs
in the following five phases:
1. Hydrolysis and acidification: This phase of aerobic decomposition lasts less than
a month or so—after the cell is covered until the exhaustion of available oxygen.
2. Acid fermentation: This phase of anaerobic decomposition lasts for years, even
decades, with the production of organic acids (namely acetic, proprionic, and
butyric acids). It is characterized by a BOD-to-COD (chemical oxygen demand)
ratio of more than 0.7, a pH level of 5–6, strong odors, ammonia concentration
greater than 500 mg/L and dissolution of heavy metals such as iron, manganese,
zinc, calcium, and magnesium.
3. Methanogenesis. This phase, in which the organic acid products of acid fermen-
tation produce methane, takes many years or even decades. The end product has
relatively low BOD values and BOD-to-COD ratios, yet it has high ammonia,
continuing metal dissolution and precipitation, and circumneutral pH.
4. Progressive stabilization: This phase is characterized by a slowdown of bacterial
decomposition with exhaustion of organic material.
5. Final storage: In this phase, decomposition is complete (McBean and Rovers 1999).
Activated sludge treatment and aerated lagoons have been effective in treating
landfill leachate. Constructed wetlands are most effectively used only as a polishing
step after lagoons for improving treatment efficiency. Constructed wetlands are
unable to treat the high concentration of ammonia present in the leachate due to
insufficient oxygen transfer rates. Thus, aerobic pretreatment of the leachate is
necessary prior to its entry into a wetland system, which results in a multi-stage
treatment process (Schwarzenbeck et al. 2003; Birbeck et al. 1990; Mæhlum et al.
2002; DeBusk 1999).
Active wetland treatment systems have been successfully used to treat leachate
directly, but only with a mechanism to boost oxygen transfer in order to oxidize
the high concentrations of ammonia commonly found in landfill leachates (Vasel
et al. 2004). FWS wetlands can remove the high ammonia in leachate; however, they
are handicapped by lower nitrate reduction. Thus, a better wetland option is an
aerated VSB wetland (Kadlec 1999; Liehr et al. 2000; Urbanc-Bercic 1994; Kinsley
et al. 2002).
Oil and Grease-Rich Wastewater
Wetland vegetation is very effective at removing oil and grease in stormwater

(domestic or industrial). In fact, studies have reported the successful removal of
BP diesel-range organics (in the C-10 to C-26 range) through horizontal-flow
vegetated subsurface-flow wetland cells in VSB systems; the removal was found
to be in proportion to the vertical distribution of roots and rhizomes in the wetland
cell (Wass and Fox 1993; Omari et al. 2003). Similarly, petroleum-containing
wastewaters are rich in volatile organic compounds and are mostly released from
loading facilities or containment areas (with relatively high concentrations during
rain and relatively low concentrations during the pumping of contaminated ground-
water). This wastewater was reported to undergo natural degradation in both FWS
and VSB constructed wetlands through a microbial community associated with the
plant rhizosphere (Wemple and Hendricks 2000; Schnoor et al. 1995; Pardue et al.
2000; American Petroleum Institute 1998).
FWS wetlands can be effectively coupled with mechanical treatment systems when
there are higher concentrations of petroleum hydrocarbons in wastewater (Lakatos
2000). VSB wetlands have been found to have greater efficiency and robustness than
FWS wetlands because of their higher biological treatment per unit area (Kadlec and
Knight 1996). In fact, the installation of adequate aeration has been found to enhance
both volatilization and hydrocarbon degradation (Kadlec 2001b).
Pulp and Paper Wastewater
The preparation of wood pulp requires a high-temperature environment to dissolve the

lignin in raw wood and thus isolate the cellulose fibers, using either a strongly alkaline
sodium sulfide solution (Kraft process) or a mildly acidic bisulfate salt solution (sulfite
process). Furthermore, bleaching may occur using chlorine, chlorine dioxide, sodium
hydroxide, oxygen, or hydrogen peroxide to manufacture a bright-white product
(Thut 1993). The dark-brown color-forming compounds of pulp wastewater (called
refractory organics) are mostly resistant to microbial degradation, with residual BOD
(approximately 10–100 mg/L after reduction from 200–800 mg/L).
Maryville Mill, a paper manufacturer in Victoria, Australia used aerated lagoons

and activated sludge basins in pioneering research on lignosulphonate, color, Total
suspended solid (TSS), BOD, and foaming tendency. The mill used wetland plants in
a partially-vegetated facultative treatment pond to treat pulp and paper mill waste-
waters with five emergent wetland plant species in FWS basins, resulting in signif-
icant pollutant removal (Allender 1984). In fact, increased retention time was also
found to result in higher removal efficiencies of TSS, BOD, NH4-N, org-N, and
phosphorous (Thut 1993). Constructed wetlands have the advantages of avoiding
residual solid management, enhancing wildlife habitats, and allowing for limited
public use of the facilities.
Acid Mine Drainage
Acid mine drainage contains high concentrations of dissolved metals from the
excavation and exposure of sulfide minerals, such as pyrite (FeS2) and Fe+2. This
drainage often enters aquifers and raises the pH (to between 4 and 7) through
buffering by mineral dissolution. Ferric oxy-hydroxide precipitates may form, thus
lowering the pH again to less than 3 (Benner et al. 1999; Brodie et al. 1993). This
low pH is the best condition for a dissolution of a wide array of metals available in
the vicinity, such as nickel, lead, manganese, copper, aluminum, and zinc.
FWS wetlands are commonly used to oxidize iron and manganese to insoluble
precipitates, which are two major components of acid mine drainage (Kleinman and
Girts 1987; Mays and Edwards 2001; Weider 1989; U.S. EPA 1993). FWS systems
are more effective than VSB systems at oxidizing iron and manganese due to their
higher oxygen transfer rates; furthermore, they have far greater storage capacity for
accumulated iron and manganese sludge because of their larger dimensions. How-
ever, poorly designed FWS wetland hydraulics can adversely affect the performance
through short-circuiting.
Some heavy metals (e.g., copper, nickel, lead, zinc, and arsenic) that are often
present in mine drainage waters are also soluble at the low pH of acid mine drainage;
furthermore, they precipitate at high pH independently or co-precipitate with iron in
constructed wetlands (Morin et al. 2003; Fitch and Burken 2003; Benner et al. 1999).
During the conversion of sulfate to sulfide, which is typical in VSB wetlands with
anaerobic conditions and a continuous supply of organic matter, these metals
undergo precipitation. They are often collected using adsorbent beds of spent
mushroom compost, manure, rice hulls, sawdust, and other similar materials (Palmer
et al. 1988; Fitch and Burken 2003).
Winery Wastewater
Winery wastewater is often richer than domestic wastewater, with lower pathogen
levels and variable loading over time (being the highest during the grape-processing
period) (Grismer et al. 2003). This wastewater possess high levels of suspended
solids from grape stems, seeds, and skins. Hence, there is a need for pre-treatment
through screens or clarifiers, as well as associated facultative ponds and sand filters
(Shepherd and Grismer 1997; Grismer et al. 2003). A typical VSB wetland is best
suited for treating winery wastewater (Grismer et al. 2003).
Limitations of Wetland Systems
Although constructed wetlands can provide low-cost and low-maintenance biolog-

ical treatment of wastewaters, the major drawback of these systems is their variabil-
ity in treatment efficiency. Much of the variability can be attributed to inadequate
knowledge of the system dynamics. Furthermore, the dominant physical, chemical
and biological processes have not yet been optimized (Cooper and Findlater 2013).
Constructed wetlands are very complex systems with variable interplay of both
external factors (e.g., flow rate, wastewater composition, temperature) and internal
factors (e.g., bacteria growth and development). Hence, these systems are mostly
regarded as “black-box” models, which can be simulated using only input and output
data and incorporate few degradation models (Rousseau et al. 2004; Wynn and Liehr
2001; Samsó and Garcia 2013). At present, no direct observational methodologies
are available to assess the systems; efforts in this direction would involve sophisti-
cated and expensive instrumentations (Mburu et al. 2013).
FWS wetlands are a known source of carbon dioxide (CO2), methane (CH4), and
nitrous oxide (N2O). Hence, they are potential contributors to global warming
(although their global warming potential is widely variable, poorly quantified due
to data scarcity, and poorly quantifiable as well) (Bartlett and Harriss 1993;
Bridgham et al. 2006; Gleason et al. 2009; Sha et al. 2011; Brinson and Eckles
2011). However, compared with natural wetlands, constructed wetlands seem to
have less soil organic matter, shorter hydroperiods, more aerobic soil conditions, and
hence lower fluxes of greenhouse gases (Bruland and Richardson 2005; Knutsen and
Euliss 2001). In fact, some authors have argued that the water quality and biodiver-
sity benefits obtained from constructed wetlands may outweigh their potential
negative impacts due to greenhouse gas emissions (Hopple and Craft 2013; Marton
et al. 2014).
Operation and Maintenance of Constructed Wetlands
A constructed wetland can be indigenously constructed using local materials. It

involves minimal usage of mechanical equipment (as well as the accompanying risks
of failure and malfunction). The constructed wetland is often scalable for smaller
units and sustainable with variable flow rates and loading conditions. Thus, it can
produce a consistent effluent quality, without constant tweaking and adjustments.
Overall, a constructed wetland is an attractive option for decentralized wastewater
management (U.S. EPA 1997; Wallace and Robert 2006). In comparison to mechanical
treatment works, wetland systems have very few operational controls because they rely
largely on passive treatment mechanisms.
Operation and Maintenance of FWS Wetlands
Control of the Water Level

In an FWS wetland, adjustment of the water level plays a critical role. The growth of
wetland plants must be accommodated during the plant establishment phase. Fur-
thermore, the depth should be increased during winter operations, decreased to dry
out and kill accumulated mats of filamentous algae, and decreased to minimize
odors. Hence, operation and maintenance of FWS wetlands primarily involves
adjusting the water level in the wetland cell (up or down) and varying the loading
between treatment cells (if the system has two or more parallel treatment trains)
through adjustment of hydraulic control structures. Additionally, water leakage
should be prevented to ensure the water level; thus, a watertight control structure
is recommended, such as an adjustable weir gate system or manufactured stacking
plate system for large- or small-scale systems, respectively.
For plant establishment and maintenance, water level control is also essential at
all three phases of the FWS wetland, as follows:
• Phase 1: Low water level and exposure of the rooting media (mud flat) is required
for the initial (re)planting.
• Phase 2: A gradual raise of the water should be synchronized with the emergence
of plants to allow the emergent shoots to be above the water surface at all times,
thus providing the plants with access to sunlight and oxygen. The required degree
of adjustment to the water level is inversely related to organic/nutrient loading.
(The maximum should be less than 2 cm/day.)
• Phase 3: The water level is maintained at the design depth upon establishment of
the wetland plants.
Winter Operations
The water level should be raised during winter months (especially in temperate
climate) to partially enhance the season-induced low biological activities. In colder
periods, the raised water may form an ice layer. In this case, the water level should be
lowered below the ice layer to create an insulative air layer below the ice layer, thus
providing warmth to the wetland. A rapid increase of the water level when an ice
cover has already formed should be avoided to prevent the plants from becoming
loose at the rooting media. An early spring rain may naturally create such a
condition; hence, frequent checks are crucial until the ice layer has melted.
Algae Control
Filamentous algae mats can displace emergent wetland plants in FWS systems,
especially with high nutrient loadings and poor establishment of emergent plants.
This may reduce the dissolved oxygen and sunlight below the algal mat, with
subsequent deterioration of the wetland plants. In such a case, the water level can be
lowered to expose the rooting media and cause removal of the algal mat through
oxidation. This should be followed by fresh replantation and increases to the water
level along with the growth of emergent plants.
Odor Control
FWS systems have an anaerobic zone at the bottom of the water column, which may
release hydrogen sulfide or other odiferous compounds. The odor may increase with
higher organic loading of the influent due to improper or only primary treatment,
turbulence, or splashing at the inlet. Streamlining the inlet flow, improving
pre-treatment before entry to the wetland, and making the wetland depth shallower
(allowing better oxygen mixing) can help to reduce the odor.
Mosquito Control
A mosquito population decreases exponentially with increasing distance from the
breeding ground (although they can travel up to 5 km from the breeding ground)
(Service 1993). FWS wetlands have dense vegetation, heavy accumulation of plant
detritus (as with most emergent wetland vegetation, such as cattail, bulrush, and
common reed), and shallow berms, which provide ideal conditions for mosquito
production; however, these are also the ideal conditions for wetland efficiency
(Knight et al. 2004; Sinclair Knight Merz 2000). Efforts to control mosquitoes
through deeper habitats, steeper berms and more open water adversely affect the
life of the emergent plants and decrease the biofilm surface area (plant detritus)—and
thus decrease wetland efficiency. Therefore, mosquito control and treatment effi-
ciency have to be a tradeoff (Russell 1999; Martin and Eldridge 1989; Kadlec 2003;
Knight et al. 2004).
Because egg-laying by adult mosquitoes is difficult to stop, favorable conditions
should be created for mosquito larva predators—such as certain aquatic insects and
select fish (e.g., Gambusia holbrooki, top minnows)—to access the entire wetland
with no depositional plugging, especially at the inlet. This is an effective method of
mosquito control that does not compromise wetland efficiency. However, in cold
climates and with less dissolved oxygen in wastewater, most of these predators
cannot survive, although mosquito larva can (Greenway and Chapman 2002;
Stowell et al. 1985). Two bacteria strains—namely, Bacillus thuringiensis
israelensis and Bacillus sphaericus—can be applied to wetlands (either in pellet or
granular form) for significant control of mosquito production (Williams et al. 1996;
Knight et al. 2004).
Vegetation Management
The removal of excess plant detritus can help with weed and mosquito control;
however, this disrupts wetland operations and creates additional problems with
regard to their disposal and the prevention of further regeneration, thereby leading
to no long-term benefits (Williams et al. 1996; Knight et al. 2004; Thullen et al.
2002). The controlled burning of excess wetland biomass (and even weeds and
invading vegetation growing in the wetland or its berms) seems to be the most
effective means of vegetation control. This approach allows for the reintroduction of
nutrients (in the form of ash) into the water column, although it does temporarily
affect the efficiency of the wetland (Kadlec and Knight 1996; Knight et al. 2004).
Management of Animals and People

Some herbivores, such as muskrats (Ondratazibethicus) and nutria (Myocastor
coypus), breed rapidly and consume emergent vegetation, such as cattails (Typha
spp.). These animals may also use the vegetation as building material for feeding
platforms and nest mounds. They can even destroy the entire wetland vegetation,
removing any ability for reestablishment through their grazing pressure and
thereby converting the wetland into a TSS and BOD-rich algal pond. Animals
may also damage the berms and dykes by burrowing. Wire mesh (chicken wire) or
armoring berms with rip-rap have been used widely to manage these animals
(Pineywoods 2001).
Similarly, beavers are attracted to flowing water for habitation. They often
construct dams and thus create plugging of outlet controls or open water runs,
which lead to hydraulic short-circuiting and a reduction in treatment efficiency.
Trapping, chain link fencing around the wetland, and exclusionary controls such
as rodent guards should be used. Common carp (Cyprinuscarpio) can also be a
nuisance species. They can uproot vegetation and disturb sediments, thereby affect-
ing treatment performance. Thus, these fish should be excluded from wetlands (Hey
et al. 1994). Even seemingly innocent birds as such as waterfowl, especially the
Canadian goose (Branta canadensis), and many resident bird populations may
consume newly planted wetland vegetation, thereby destroying the wetland. This
problem should be tackled by netting and deterring these birds, which can also
contribute to elevated fecal contamination levels in the wetland effluent.
FWS wetlands are often encroached upon by birdwatchers and outdoor enthusi-
asts who are exploring the habitats. This adds a further responsibility to provide safe
and well-lit public access with adequate parking. Specific measures such as fencing,
prohibiting children and domestic pets from entering the area, and the provision of
signboards may also be required in providing risk-free access for people while
protecting the ecology of the environment (Kadlec and Knight 1996).
Operation and Maintenance of VSB Wetlands
Control of the Water Level

Similar to FWS wetlands, water level adjustments in a VSB wetland (or between
splits for parallel cells, if any) are crucial, especially in those using gravel as bed
media. The wetlands should have no leaks, with the water level below the soil yet in
contact with the root zone, with the vegetation having poor drought resistance.
Because the water in this system is not visible, its operation requires more intuition
and experience than does an FWS wetland.
For plant establishment and maintenance, water level control is also essential in
all three phases of a VSB wetland, as follows:
• Phase 1: The water level should be maintained at a fixed level before plantation to
ensure that it is in contact with the rootstock during the plant establishment; this
helps to avoid exposure of the rootstock to the sun, which leads to wilting.
Furthermore, it should be ensured that vegetation is not unable to access the
water on its own due to the poor capillary action of gravel. As the plants grow,
fluctuations in the water depth need to be managed to enhance root penetration
into the bed media.
• Phase 2: The water level should be lowered gradually to the design’s water level
after the establishment of wetland vegetation. Lowering the water level incre-
mentally assists with deeper root penetration into the VSB bed.
• Phase 3: The water level should be kept in contact with plants, yet below the soil
level, for plants that are already established.
Odor Control
A VSB wetland system often involves only primary treated effluent (mainly from a
septic tank). Thus, the water level needs to be minimized to prevent the odors
resulting from anaerobic decomposition, except if a VSB system is covered with
insulating and odor-arresting mulch layers.
Winter Operations
In cold but not freezing climates, no insulation is necessary. However, temporary or
permanent insulation of hay, straw, or leaf litter, among others, can prevent a VSB
wetland from freezing. If the insulation materials are degraded, however, they may
break down and thereby adversely affect treatment. The water depth should be
decreased during the winter to create an insulating air gap. The most critical point in
a VSB system is the outlet water control structure, as it is most susceptible to freezing;
thus, this point needs to be monitored to avoid clogging, insulated, and (in severe
freezing conditions) heated through an electrically powered source (e.g., incandescent
light bulb, stock tank heater) (Kadlec and Knight 1996; Wallace et al. 2001).
Bed Clogging
Clogging is a major constraint of a VSB system as it obstructs the flow. Thus, the
operator should carry out a series of troubleshooting steps to assess the cause, as
there is a lack of visual cues (unlike FWS wetlands).The troubleshooting steps
should involve the following:
• Checking the outlet valve for scum clogging

• Checking the surge adequacy for surfacing (which may be confused with
clogging)
• Checking the daily flow rate and proper dimensioning to prevent flooding
• Checking the adequacy of organic loading across the cross-sectional area and
influent suspended solids levels of the wetland, which can lead to precipitation
and clogging
• Checking the influent iron levels (especially for landfill leachate, which are
normally rich in iron), as this causes oxidation and precipitation
• Checking the system hydraulics

• Observing deliberate fluctuation (over a day or longer) and corresponding
response of the wetland
A basic strategy for addressing a VSB clogging problem includes the following:
• Replacing the connecting septic tank baffles (if non-functional or missing) so that
they are adequate for handling the pumping rate
• Reducing surges at the inlet end of the VSB by reducing the pumping rates and
dose volumes (including pretreatment of influents if they are rich in BOD,
suspended solids, or iron)
• Replacing clogged VSB media with new (preferably coarser) bed media
• Adjusting the influent distribution header to create a higher cross-sectional area
(at the header/media interface)
Undesirable Plant Species

A layer of mulch and/or plant detritus on top of a VSB wetland may lead to the
invasion of undesirable plants into the wetland system. To solve this problem,
complete coverage of the desired plant species should be maintained, with no
space for invaders. Any invaders can be controlled locally by hand weeding and
spot applications of herbicides. Some common invaders of VSB systems that receive
full sun include cottonwood (Populus deltoids), giant ragweed (Ambrosia trifida),
Canada thistle (Cirsium arvense), and marijuana (Cannabis sativa). Stinging nettle
(Urtica dioica) and jewelweed (Impatiens capensis) commonly invade VSB systems
that receive partial sun.
Cost of Wetland Treatment Systems
Wetland systems generally use local labor and local materials. Hence, a standardized
cost estimation cannot be applied to all treatment systems. The cost of the basic
components of a wetland treatment system, such as earthwork, gravel (for VSB
wetlands), and plants, are distance sensitive. Labor costs are also widely variable.
However, in determining the economic feasibility of a wetland treatment system,
local cost figures (involving capital and operating costs) can be used to compare
various treatment technologies.
Conclusions
The use of constructed wetlands for domestic wastewater treatment has increased
exponentially in recent years, especially for small-scale decentralized units in indi-
vidual homes and small communities. Wetland systems have been constructed
extensively across the globe to treat a wide range of wastewater types. However,
the reliability of the effluent quality is still unclear because their dynamics are not
well understood. However, as a passive treatment unit, a constructed wetland is the

most environmentally friendly treatment option. Performance monitoring and
reporting requirements vary widely spatiotemporally, especially for small-scale
systems, so a centralized repository of information on wetland systems does not
exist. Many small-scale wetland designs are based on intuition, best practices, or
borrowed designs from other treatment technologies (e.g., facultative lagoons).
Hence, a deeper exploration of the feasibility of constructed wetland systems and a
better understanding of the dynamics of this green approach are required for
synergistic networking and standardization of the system specifications.
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How to Improve Selectivity of a Material
for Adsorptive Separation Applications 61
Vipin K. Saini and Aparajita Shankar
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1470
Adsorption Technique and Adsorbent Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1470
Role of Adsorbent in Different Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1471
Industrial Wastewater Treatment Using Low-Cost Materials as Adsorbent . . . . . . . . . . . . . . . 1473
Adsorption Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1475
Post-modification of Adsorbents to Improve Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1476
Chemically Modified Natural Adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1478
Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1478
Improvement in Adsorption Selectivity of Natural Zeolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1479
Modification in Natural Clay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1482
Chemically Modified Chitosan as Biomaterial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1485
Agricultural Waste Adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1489
Soil/Silica Adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1492
Metal-Organic Framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1493
Future Prospects of Modification Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1495
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1496
Abstract
This chapter analyzes how adsorption selectivity of natural and synthetic mate-
rials was improved with different approaches, particularly for their adsorptive
water treatment applications. To explain this approach, it includes some of the
frequent modification in natural materials like activated carbon, natural zeolite,
natural clay, biopolymer (like chitosan, cellulosic waste), sand, and some of the
post-synthetic modification in materials like metal oxides, mesoporous silica, and
metal-organic frameworks (MOFs). Herein, different types of modification
approaches applied to an individual category of material were reviewed,
V. K. Saini (*) · A. Shankar

School of Environment and Natural Resources, Doon University, Dehradun, Uttrakhand, India

https://doi.org/10.1007/978-3-319-73645-7_43
1470 V. K. Saini and A. Shankar
systematically. The effects of these modifications on surface area, porosity,

adsorption capacity, and surface chemistry were discussed in terms of change in
their adsorption selectivity. For instance, it comprises impacts of oxidation,
sulfurization, nitrogenation, and coordinate ligands on the surface properties of
activated carbon. Similarly, the role of metal ion, surfactant cations, metal oxides,
and polymers on the change in ion exchange properties of zeolites was explained.
The change in physicochemical properties of clay on thermal treatment and
treatment with ionic and organic species was compared. Likewise, the adsorption
selectivity of the clay-based composite with different polymers and effects of
modification of chitosan, agricultural by-products, sand, silica, metal oxides, and
MOFs were deliberated. In the end, some of the future challenges in the field of
adsorption selectivity are discussed.
Keywords
Adsorption technique · Adsorbent materials · Activated carbon · Natural zeolite ·
Chitosan · Biomaterial · Metal-organic framework
Introduction
Adsorption Technique and Adsorbent Materials
Adsorption is a universal process, which has long been considered as a competent

loom for pollutant control. This process occurs when a gas or liquid solute makes a
molecular or atomic film (adsorbate) on the surface of a solid or liquid (adsorbent)
(Fig. 1). It is operational in most natural physical, biological, and chemical systems,
widely in the field of industrial wastewater treatment because of its simplicity and
cost-effectiveness. This process is generally classified into physical adsorption (due
to weak van der Waals forces) and chemical adsorption (due to covalent bonding).
Adsorption can also occur due to electrostatic attraction. The adsorption by adsor-
bent materials is a classical technique for water treatment. It is useful for the removal
of organic as well as inorganic pollutant from wastewater. There are many other
methods like coagulation, precipitation, ozonation, reverse osmosis, ion exchange,
and advanced oxidation processes available for the purification of polluted water and
wastewater. Adsorption processes do not produce harmful by-products. Further, it
has advantage over the other methods because of its economical and simple design.
In every adsorption-based process, adsorbent plays a critical role. In general, an
adsorbent material is characterized by its large specific surface area, pore size
distribution, and surface polarity (surface functionality). A large number of adsor-
bents are available for adsorption application. All these adsorbents can be catego-
rized in a number of ways. One of the classifications is in terms of natural adsorbents
and synthetic adsorbents. The natural adsorbents are those which can be extracted
from the nature like clay materials, natural minerals, metal oxides, cellulose, natural
fibers, and many others. These materials are eco-friendly, low cost, and rich in
supply, whereas those adsorbents which are not found naturally can be prepared
61 How to Improve Selectivity of a Material for Adsorptive Separation. . . 1471
Fig. 1 Adsorption
phenomenon
ADSORBATE ADSORPTIVE
ADSORBENT
chemically, known as synthetic adsorbents. At present, several synthetic adsorbents

such as synthetic resin, synthetic zeolites, synthetic carbonaceous adsorbents,
and polymeric adsorbents are frequently in use. The selectivity of natural adsorbents
is slighter than the synthetic ones; however the selectivity and adsorption capacity
of natural adsorbent or even synthetic adsorbents can be improved by further
modification in their structural properties.
Role of Adsorbent in Different Technologies
The adsorbents have various applications in different areas of science and research as
shown in Fig. 2. The versatile physicochemical properties of these adsorbents make
them ideal choice for a number of important technologies. Some of the important
technologies are discussed here below.
In the gas separation application, adsorbent materials selectively capture the gas
from the gases stream bought into contact to its surface (Velu et al. 2003). Adsorptive
separation of many gaseous pollutants like NOx, SOx (due to the combustion of
gasoline, jet fuel, and diesel fuel), natural gases, and hydrocarbons such as CH4, N2,
CO2, H2S, and He has been reported in the literatures (Du and Zou 2016; Misra et al.
2016). In petroleum refinery process, deep hydrosulfurization with the conventional
hydrotreating technologies (HDS. removal of sulfur; HDN, removal of nitrogen) is
applied for the removal of nitrogen and sulfur, found in the gas oil, over the novel
polymeric adsorbent prepared by using unsaturated polyester resins (UPR), glycidyl
methacrylate (GMA), and divinylbenzene (DVB) as monomers (Al-Daous and Ali
2012). Alumina immobilized with Ni and Mo is also widely used in industry for
hydrotreating the gas oil (Toni Raabe et al. 2014). However for removal of pollutants
from the natural environment, the adsorption on the surface of zeolite immobilized
with (Cu, Pb, Zn, Ni, Ca) ions and modified active carbon, silica, and metal oxides
has been reported. Iron-based adsorbent has been used for removal of H2S and
oxygen from biogas (Shimekit and Mukhtar 2012). In spite of gas separation, the
adsorbent is also being used in gas purification technology.
In gas purification technology, the use of cyclic thermal swing adsorption is a
widely applicable process for CO2 removal from natural gas or drying (Mersmann
et al. 2011). Mostly the temperature swing adsorption is applied on the molecular
Photocatalysis Biomedical Science
Drug
Photocatalyst
Nanoparticle Drug loaded nanoparticle
Reverse
Waste water Clean water osmosis
Nanofiltration
Ultrafiltration
Microfiltration
E.coli Viruses Ions

Oil Proteins
Small
Macromolecules compounds
Colloids
Suspended particles
Water Treatment
Gas separation & Purification
Fig. 2 Application of adsorbents in different technologies
sieves loaded with H2O, SO2, and CO2. The TSA process is also applied for the
regeneration of activated carbon, zeolites, and silica gel loaded with hydrocarbons
present in natural gas (Cavenati et al. 2006). Zeolite as microporous material
preferentially absorbs CO2, which is mostly used in pressure swing adsorption
(PSA) processes. Zeolites, due to their higher selectivity for CO2, are preferred
over other adsorbent (activated carbon) for this purpose (Worch 2012).
From ancient Greece times, the adsorbents are being used for purification of
drinking water. Since then, this technique has been continuously used for water
treatment with new improvements from time to time. Adsorption-based water
purification technologies are efficient for removing specific types of impurities
down to very low levels in the parts per billion (ppb) and parts per trillion (ppt)
ranges. The application of activated carbon has proven it as good adsorbent for the
removal of wide range of water pollutants such as phenols, chlorinated hydrocar-
bons, pesticides, pharmaceuticals, personal care products, corrosion inhibitors, and
so on (Yang et al. 2016a). Fibrous filters and activated carbon filters are also used as a
tertiary treatment process in drinking water purification. Ion exchange technique for
the purification of water by porous beads as adsorbent prepared from highly cross-
linked insoluble polymers with large number of strongly ionic exchange sites is also
an important technique for the removal of charged ions from water.
In the field of medical science, adsorbents in the form of nanoparticles are used as
a drug carrier for the treatment of diseases. To transmit adequate dose to the lesion,
suitable carrier of drugs is needed. Nano- and microparticles such as chitosan, drug-
clay nano hybrid (Torres et al. 2016), carbon nanotubes (Tamayo et al. 2015),
mesoporous silica (Wang et al. 2015a), and carbon nano fiber (Kumar 2000) carrier
have important potential applications for the administration of therapeutic mole-
cules. Controlled drug delivery technology offers various advantages over the
conventional dosage forms, which includes improved efficacy, reduced toxicity,
and improved patient compliance and convenience. Synthesis of polymeric nano-
sphere micelle based on biocompatible copolymer of poly (ethylene oxide)-poly
(L-Lactic acid)/poly(β-benzyl-L-aspartate) has been tested as a vehicle for delivery
of anti-inflammatory and antitumor drugs (Borges et al. 2016).
Adsorbents are good catalytic supports due to their large surface area. In hetero-
geneous catalysis, the active catalysts are often supported/incorporated on the
surface of adsorbents. It improves the efficiency and recovery of these catalysts
during catalytic reaction. Photodegradation by the photocatalyst-loaded adsorbents
for the removal of organic pollutants from the wastewater has been reported in the
literature. Activated carbon developed from several sources such as natural mineral
material (Etim et al. 2015), coconut shell, rice husk, and bark has been immobilized
with TiO2 which has also been reported for the removal of phenol from water.
Combination of UV radiation and TiO2 gave a reasonable degradation efficiency
(Ijaola et al. 2013). Pure chitosan has been grafted with ZnO photocatalyst to obtain
ZnO/Cht-MCM. This material can be used for photodegradation of azo dye and
methyl orange from the aqueous solution.
Industrial Wastewater Treatment Using Low-Cost Materials

as Adsorbent
Sudden increase in population, rapid urbanization, industrial and technological

expansion, energy utilization, and waste generation from domestic and industrial
source have rendered many noxious and hazardous waste into the environment
which are harmful to human health as well as the aquatic life. Inadequately treated
wastewater or untreated discharge by the industries into the water ways is the main
cause of water pollution. Industrial wastewater is often contaminated with numerous
compounds, for example, heavy metals, dissolved organic compounds, suspended
solids, etc. Industrial discharges resist the self-purification capabilities of the river as
well as decomposition in wastewater treatment plant (Ademiluyi et al. 2009; Khan
et al. 2016). Therefore, it is imperative that it should be treated to an environmentally
acceptable limit. The physicochemical processes have proven useful tool for selec-
tive removal of organic and inorganic pollutants from the wastewater.
Various natural occurring materials are present in large quantity having properties
of adsorbents. The abundance of these materials and their low cost actually make
them suitable as an adsorbent for the removal of various water pollutants. Their
naturally occurring adsorbents involve clay, sand, charcoal, chitin, agricultural
by-products and natural zeolites, etc. Although all these types of materials are
abundant in nature, their use is often limited, due to their poor adsorption properties.
Some of the natural adsorbents used for wastewater treatment are discussed below.
Activated carbon prepared from different natural source materials (e.g., bamboo,
rice husk, peanut hull, coffee husk, coal, coconut shells, lignite, wood, etc.) is the
most popular and widely used adsorbent in the field of wastewater treatment
throughout the world. Removal of pollutants such as dyes (Kumar and Jena 2016),
phenols (Ibrahim et al. 2016), heavy metals (Saygili and Guzel 2016), pharmaceu-
tical drug (Salman 2014), pesticides (Water Treatment Using Carbon Filters: GAC
Filter Information 2004), fertilizers, detergents, oil, and greases has been reported on
this type of materials. Post-modification of materials improves properties toward
pollutants. A filter with granular activated carbon (GAC) is a proven option for
the removal of chemicals that give objectionable odors or taste of water such as
hydrogen sulfide (rotten egg odor) or chlorine.
Excess release of heavy metals in aqueous waste of many industries such as metal
plating, tanneries, radiator manufacturing, alloy industries, mining operation, and
storage batteries has created an environmental problem worldwide. There are
numerous reports available involving heavy metal removal using natural adsorbents
developed from agricultural waste or industrial by-products. Various natural adsor-
bents such as chitosan (Turan et al. 2014), peat (Poots et al. 1976a), wood (Poots
et al. 1976b), natural coal (Kong et al. 2016), natural clay (Yang et al. 2016b),
sawdust (Al-Riyami et al. 2014), and zeolite (Mudasir et al. 2016) have been
reported for the removal of dyes, heavy metals, and phenols (Su-Hsia Lin and
Juang 2009) from the wastewater.
Nowadays, the use of adsorbents prepared from low-cost agricultural waste has
been increasing for the purification of water (Fig. 3). Various studies on adsorbents like
rice husk, neem bark, waste tea, walnut shell, maize leaf, sago waste, etc. have been
also reported in literature. Important benefits of using agricultural waste in wastewater
treatment include easy technique, modest processing, reasonable adsorption ability,
Adsorbed Pollutants
H2O In
H2O Out
Adsorbent Material
Fig. 3 Water treatment using adsorbent material as a filter

economical, easy availability, and regeneration. On the other hand, the use of untreated
agriculture waste can fetch problems of COD, BOD, and TOC in water and make them
suitable for aquatic life (Tripathi and Rawat Ranjan 2015).
Widespread industrial activities are producing large amount of solid waste mate-
rials. Some materials are being put to use, and some get dumped elsewhere. The
industrial by-products can be found easily in free of cost. The dumping of solid
waste is also an environmental issue. So, one of the best ways to reduce the solid
waste is to use these wastes as an adsorbent material. With this view, several
industrial wastes are being investigated with or without treatment as an adsorbent
for wastewater treatment. The use of fly ash produced as a by-product from the
thermal power plant has been investigated for the removal of phenol and its analogue
(Sarkar and Acharya 2006). Other industrial wastes such as blast furnace slag, dust,
and sludge (Chazarenc et al. 2010) from steel industry and red mud (López et al.
1998) from aluminum industry have also shown considerable effect for the removal
of heavy metal pollutants from wastewater.
Adsorption Selectivity
The preferential adsorption of a component on over an adsorbent surface from the

mixture of components is termed as its adsorption selectivity. The adsorption
selectivity is usually controlled by two factors. One of which is surface functiona-
lization. The functional groups present on the surface of adsorbents interact differ-
ently with different molecules from the adsorbate mixture. The extent of interaction
is related with the functional groups present on the adsorbate molecules. This leads
to preferential adsorption of most interactive molecules on the surface of adsorbent
and thereby causing separation. The other factor that controls selectivity in some
cases is the pore size of adsorbents. This phenomenon is also called as size
exclusion. In this process the molecule that matches the size of pores is able to
enter in pores and gets adsorbed, whereas others remain in adsorbate mixture. This
phenomenon is often observed in controlled pore size materials like zeolites and
metal-organic framework (MOFs). The adsorption selectivity is a useful property of
an adsorbent particularly for its application in separation and purification process.
Separation of pure gas such as CO2 and CH4 from the gas mixture is achieved by
using microporous MOFs. The MOF is prepared by mixing ligands, and the resulting
material demonstrates higher selective CO2 uptake over CH4 (Misra et al. 2016). The
new porous tetrahedral Zn(II)-tetrazolate framework exhibits high CO2 adsorption
selectivity over N2 (Li et al. 2016). Microporous MOFs (HKUST-1) have also been
used for competitive adsorption and selectivity of benzene and water vapor, and it
was found that the benzene molecule is more selective than water vapor at high
temperature and pressure (Zhao et al. 2015).
The hyper-cross-linked polymeric adsorbent of NDA-100 is more selective for
salicylic acid as compared to amine-modified NDA-99 which solves the discharge
pollution problem resulted from esterification process (Liu et al. 2007). Discharge of
radioactive elements into the environment through nuclear waste effluents, nuclear
weapon testing, and nuclear power accidents contaminates agriculture soil, water
body, and crops. Adsorptive selection of the radioactive elements like Cs and Sr from
the environment on the several zeolite materials is also been reported in the literature
(Munthali et al. 2015).
Adsorption selectivity is also very important for selective removal of emerging
water pollutants like pharmaceutical drugs. A study had shown the removal of
nonsteroidal anti-inflammatory drugs (naproxen, ibuprofen, and diclofenac) on the
surface of molecularly imprinted polymer adsorbents. It was found that the extrac-
tion efficiency of MIP was higher than those obtained when non-imprinted polymer
was used as adsorbent. The synthesized MIP had proven higher selectivity to
diclofenac rather than naproxen and ibuprofen (Trinh et al. 2016).
Hydroquinone-modified porous adsorbents have been studied for simultaneous
separation and purification of (EGCG) ()-epigallocatechin gallate, and caffeine
(CAF) from crude extract of green tea was established by size-exclusion effect. The
result showed that the hydroquinone-modified porous adsorbent provided the best
separation power due to its porous structure and phenolic hydroxyl group (Zhang
et al. 2016a).
Post-modification of Adsorbents to Improve Selectivity
As there are many natural and synthetic adsorbents available for the purification,
separation, and removal of pollutants from water and gases stream, the modification
of these adsorbents is gaining prominence to increase their affinity for certain
contaminants to facilitate their removal from the mixture stream. To increase effi-
ciency the adsorbent materials are processed by both physical and chemical treat-
ment. Physical treatment includes freezing, boiling, heating, lyophilization, etc.,
whereas chemical treatment involves cross-linking with organic solvents, washing
with detergents, chemical reaction with a variety of organic and inorganic com-
pounds, alkali or acid treatment, etc. (Farooq et al. 2011). The pretreatment modifies
the surface characteristics of adsorbents by exposing more metal binding sites
(Vieira and Volesky 2000). Post-modification process tailors the surface property
of adsorbents such as surface area, surface charge, pore volume, pore size, and fast
adsorption kinetics. Adsorbents such as zeolite, activated carbon, natural clay,
low-cost materials, MOFs, MCM-41, and SBA-15 had been post-modified to
improve its adsorption capacity. In the literatures, successful synthesis of
carboxymethyl chitosan modified with magnetic-cored dendrimers (CCMDs) for
the removal of methylene blue (MB) and methyl orange (MO) has been reported.
Dendrimers are hyper-branched molecules that possess excellent properties of nano-
size and facile surface modification (Calabretta et al. 2007). Because of their
dendritic structures, they contain much higher functional group densities than
conventional macromolecules. To enhance the application of dendrimer-based sor-
bents, various materials such as silica gel (Niu et al. 2013), mesoporous silica (Jiang
et al. 2007), natural clay (Zhou et al. 2015), fiber (Zhang et al. 2013a), grapheme
oxide (DeFever et al. 2015), etc. have been modified (Kim et al. 2016). Adsorptive
removal of organophosphate insecticide (Azodrin) onto biopolymer-modified mont-

morillonite (MMT)-CuO composites, viz., MMT-Cuo-Chitosan(ch), MMT-CuO-
Gum ghatti(Gg), and MMT-CuO poly lactic acid (PLA), has also been studied in
literatures (Sahithya et al. 2016). In addition, cross-linked chitosan magnetic beads
modified with cysteine-glutaraldehyde Schiff base (Chi-CG) were utilized as a
possible adsorbent for the elimination of Cu (II) and Cr (VI) from aqueous solutions
(El-Reash 2016).
Post-modification of other natural adsorbents increases their adsorption perfor-
mances and permitted an easy separation of pollutants from wastewater (Fig. 4).
Zeolite with silver nanoparticle increased the removal of E.coli and heavy metals
(Pb, Cd, and Zn) in a continuous flow system (Akhigbe et al. 2016). Selectivity of
toxic metal ion Hg(II) has also been investigated on the natural zeolite surface
immobilized with dithizone in the toluene medium and shown a high adsorption
capacity (Mudasir et al. 2016). To obtain the heterogeneous Fenton-like catalyst,
inexpensive adsorbent iron-modified bentonite had been prepared by wet impregna-
tion method to rapidly remove the organic pollutant (rhodamine B) from aqueous
solution. In another work, natural magnetite ore was modified with aluminum and
lanthanum ions to increase the fluoride removal efficiency from waste water (García-
Sánchez et al. 2016). Treatment of commercial activated carbon as well as activated
carbons prepared from wastes and by-products to improve its surface property has
also been explored in the literatures (Rivera-Utrilla et al. 2011).
Surface-functionalized mesoporous materials have potential applications in various
areas such as catalysis, chromatography, metal ion extraction, adsorption, nanotech-
nology, and imprinting for metal recognition (Alothman 2012). Nitrate anion removal
from water by using an amine-functionalized MCM-41 as adsorbent is reported
(Ebrahimi-Gatkash et al. 2015). Similarly, the synthesis and post-modification of
another mesoporous silica material (SBA-15) with methyl-diethyl-amine (MDEA)
and piperazine (PZ) were also studied for CO2 separation from biogas. The adsorbent
showed good performance for separation of CO2 (Xue and Liu 2011).
This review aims to summarize the modification techniques available to improve
the adsorption selectivity of natural adsorbents. This review can serve as a report that
Unmodified structure Modified structure
Fig. 4 Image showing the adsorbent after surface modification

compares different modification techniques in view of their effects in terms of

selectivity. It also provides an overview of material-specific techniques and
application-specific techniques. It is believed that this article would be useful to
researcher in deducing a preferred modification for their objective applications.
Chemically Modified Natural Adsorbents
Natural adsorbents are abundant, low cost, and widely been used for the separation
and purification processes from the past decades. Sorption on natural surface is one
of the cheapest processes to reduce environmental pollution. Chemical modification
of these adsorbents by different techniques has shown satisfactory results in terms of
their efficiency and applications in various fields. In the surface modification pro-
cess, functional groups such as amino, aldehyde, phenol, metal oxides, hydroxyl
group, carboxyl, etc. are grafted over the surface of natural adsorbents to increase its
surface properties like adsorption selectivity, enhanced surface area, pore volume,
high adsorption capacity, and adsorption kinetics. In the following section, natural
adsorbents along with its available chemical modification techniques that have been
reported for modification of different natural adsorbents have been revised.
Activated Carbon
Activated carbon is one of the widely used adsorbent (Su-Hsia Lin and Juang 2009).
For several decades, it is used as a water industry’s standard adsorbent for the
reclamation of industrial and municipal wastewater (Kaushik et al. 2008). Activated
carbon developed from plant or animal waste and industrial by-products have shown
commendable removal efficiency over pollutants. This material is low cost, requires
little or no processing, is easily available, is biodegradable, and can be easily
disposed by incineration. Modification and impregnation techniques improve its
selectivity and removal capacity over pollutants in gases and water streams.
Modification of activated carbon can be performed by treating with oxidizing
agents, such as nitric acid, ammonium persulfate, hydrogen peroxide, etc. By this
treatment, alteration in textual property of AC and generation of acidic oxides
(carboxylic, phenolic, lactones) and/or basic groups (pyrone-like groups) occur.
Oxidized activated carbon extracted by using HNO3 as a reflux is reported in
literatures (de Mesquita et al. 2006). Likewise, activated carbon was also prepared
from olive stones and almond shells with different degrees of activation oxidized
with HNO3, H2O2, and (NH4)2S2O8 mentioned in literatures (Moreno-Castilla et al.
1995, 1997, 2000). One to 10 wt% aqueous solution of sodium dichloroisocyanurate
(DCI) was used to introduce oxygen and chlorine surface groups on activated carbon
by chemisorption (Molina-Sabio et al. 2011). Electrochemical oxidation of activated
carbon fiber has also been reported (Chiang and Chen 2010).
Sulfur modification is another technique to increase the efficiency of AC. Activity
of carbon-sulfur complexes in adsorption processes is the most important factor due
to their chemical nature. This determines during the acid-base character of carbon
surface, in such process. Activated carbon derived from nut shell had been modified
with sulfur by applying SO2 gas as sulfurizing agent (Fouladi Tajar et al. 2009). In a
different approach, AC from sugarcane bagasse was made followed by single-step
steam pyrolysis in the presence of SO2 and H2S as sulfurizing agent (Krishnan and
Anirudhan 2002).
Nitrogenation on the surface of AC increases its basicity which is a required
property for adsorption and catalysis. Depending on the reagent used, the process
was conducted either in gas (ammonia, hydrogen cyanide, and amines) or liquid
(nitric acid, urea amines, and ammonia) phase. Sometimes, the process may consist
two stages, (i) single nitrogenation stage and (ii) two successive stages in which an
AC substratum was first oxidized in liquid phase and then nitrogenation in gas or
liquid phase. To enhance the adsorption of phenol from aqueous solution, wood-
based activated carbon had been modified with nitrogenation by flowing ammonia
and nitrogen throughout the process in quartz tube (Yang et al. 2014). Similarly,
activated carbon developed from polish brown coal, bituminous and subbituminous
coals enriched with nitrogen by ammoxidation (simultaneous oxidation and
nitrogenation of fossil coals) for removal of NO, and contaminants from liquid
phase has been studied (Pietrzak et al. 2010; Pietrzak 2009). In addition,
ruthenium-based catalysts supported on activated carbon (neutral and coconut car-
bon) modified with NO2, NH2, and N-H-N groups had been assessed for their
catalytic activity for acetylene hydrochlorination, aimed to improve the activity
and stability of the acetylene hydrochlorination catalysts (Xu et al. 2015). Functiona-
lization of nitrogen onto surface of AC with nitration to improve its selectivity
for CO2 capture has been mentioned in literatures (Zhang et al. 2013b; Jennifer
Wilcox et al. 2014).
Coordinate ligands are also being used to alter the AC and the textural (surface
area, porosity) chemical properties and enhance its adsorption capacities. Modifica-
tion of AC depends on the composition of legends used. Studies show the effect of
water-soluble ligands (sodium borohydride, polyvinyl alcohol, glucose, and galac-
tose) on the preparation of nano-silver-supported activated carbon prepared from
German beech wood (Eltugral et al. 2015). Activated carbon modified with hybrid
ligands, i.e., combined treatment of nitric acid and thionyl chloride, followed by the
reaction with ethylenediamine, to introduce S-, N-, and Cl-containing functional
groups for the removal of mercury in aqueous solution had been reported (Zhu et al.
2009). To improve photocatalytic properties of coordination complex-modified
polyoxometalates (CC/POMs) in visible light region, its nanobelts were loaded on
activated carbon fiber. The resulted material (CC/POMNBs/ACF) was studied for
the degradation of rhodamine B under visible light irradiation (Lu et al. 2015).
Improvement in Adsorption Selectivity of Natural Zeolite
Zeolites are naturally occurring hydrated aluminosilicate minerals with a cage-like

structure. These materials come under the class of minerals known as “tectosilicates.”
Naturally zeolites are formed by the volcanic rocks; ash layer reacts with alkaline
groundwater and crystallizes in postdepositional environment over the years in shallow
marine basins. The structures of zeolite consist of three-dimensional frameworks of
SiO+4 and AlO+4 tetrahedral (Khachatryan 2014). The position in the center of the
tetrahedron of four oxygen atoms is occupied by the aluminum ion, and the isomor-
phous replacement of Si+4 by Al+3 lifts up a negative charge in the lattice. The net
negative charge is balanced by the exchangeable cation (potassium, sodium, or
calcium). With certain cations these cations are exchangeable in solutions such as
lead, zinc, manganese, and cadmium (Barrer 1978; Breck 1964). This exchangeable
ion makes zeolite an effective adsorbent for the removal of heavy metals in industrial
effluent water. Commonly, surface alteration of natural zeolite adsorbent is
being done using a specific and sensitive ligand to enhance the capacity and
selectivity. Different techniques are discussed under subsequent heading for the
modification of zeolites.
Metal Cation-Modified Zeolites

Zeolites are capable to exchange ions with external medium, which is one of
their remarkable characteristics. The ion exchange property of natural zeolite
depends on several factors, including ion shape, size, charge density of mineral
network, framework structure, ionic charge, and concentration of the external
electrolyte solution (Bish and Ming 2001). Natural zeolite (clinoptilolite) has been
modified with Na and Ce-Fe. To obtain zeolite-rich tuff, the adsorbent was kept in
contact with NaCl and CeCl3-Fecl3 solutions (Olguin and Deng 2016). Likewise,
activation of natural zeolites (clinoptilolite) with Na+ cation and functionalization
with barium and copper ions have also been reported (Rodrigues and Rubio 2007).
The modification involves two steps of ion exchange, (i) activation of Na-Z and
(ii) functionalization of Ba-Fz and Cu-Fz. For the activation of zeolites, powdered
material was taken in an aqueous solution. Barium chloride and copper nitrate in
aqueous solution along with activated zeolite are used for functionalization of the
materials. This process increases the exchange of cations from solution to the zeolite
framework. For disinfection and metal removal, silver modified with zeolite has also
been investigated (Akhigbe et al. 2016). Modification of natural zeolites with
surfactant cations has shown commendable effects. Cationic surfactants have posi-
tive charge head group attached with hydrocarbon moiety. To prepare cationic
surfactant-modified zeolites (CSMZ), several cationic surfactants such as tetra-
methylammonium, tetraethylammonium bromide, hexadecyltrimethylammonium
bromide or chloride, cetylpyridinium bromide, ethyl hexadecyl dimethyl ammo-
nium, and 4-methylpyridinium are mentioned in the literatures (Apreutesei et al.
2008; Krajišnik et al. 2010). Similarly, cation surfactants (benzalkonium chloride
and cetylpyridinium chloride) have also been observed for the modification of
clinoptilolite (Daković et al. 2013). In addition, Pd2+- and Ni2+-modified alumino-
silicates are used as a filter to decrease heavy metals in cigarette smoke (Afzali et al.
2007). Ion exchange on the surface of NaX and NaY zeolites modified with alkali
metal cations such as Li+, K+, Rb+, Cs+, Ni2+, and Cr3+ is studied for the adsorption
of CO2 and nitrogen (Bendenia et al. 2011; Walton et al. 2006).
Oxide-Modified Zeolites
One of the most common modifications to enhance adsorption capacity of natural
zeolite is by iron oxide. According to literature, the FeOZ has a higher specific surface
area. This characteristic makes it better than the unmodified zeolites (Doula and
Dimirkou 2008). For example, natural zeolite modified with FeO was obtained by
adding natural clinoptilolite in an iron nitrate solution under strongly basic conditions
(Doula and Dimirkou 2008). Similarly, clinoptilolite modified iron oxide prepared by
mixing natural clay into the freshly prepared solution of Fe(NO3)3.9H2O and KOH
solution followed by drying and washing. This modification increases the surface of
produced adsorbent that consists of negative charge, and this makes cations adsorb on
the adsorbent under acidic condition (Dimirkou and Doula 2008). In another study,
iron oxide-modified clinoptilolite was prepared by adding a mixed amount of (natural
clinoptilolite sodium) NC-Na into a solution containing metal and NaOH. Afterward
the sample is immersed into FeCl2 solution. This fabrication increases the metallic
species on the surface of adsorbent for the adsorption of pollutants (Trinh et al. 2016).
As the like, the Mexican natural zeolite-impregnated iron oxides were obtained by
adding zeolite into the Fe solution prepared from FeSO4.7H2O and FeCl3 salt. NH4OH
added dropwise into the suspension. This modification enhanced the pores and surface
properties of the adsorbents (Mockovčiaková et al. 2006).
Zeolites can also be modified with manganese oxides (Catts and Langmuir 1986).
In this view, to prepare the manganese oxide-modified clinoptilolite, the zeolite was
added in MnCl2 solution for ion exchange. Afterward, the ion-exchanged zeolite is
washed with water, filtered and dried, and immersed in KMnO4 solution. This
modification increases the selectivity of the adsorbent toward the guest molecules
of Zn2+ (Irannajad et al. 2015). Similarly, clinoptilolite- and bentonite-modified
MnO was formed via precipitation. For this, the samples of zeolites were stirred in
KMnO4 solution. Then, HCl is added dropwise into the solution and heated. After
titration, the product is stirred, washed, and dried. After modification the cation
exchange capacity is increased over the surface of adsorbents (Schütz et al. 2013;
Mohamadreza and Maryam 2014).
Polymer-Modified Zeolite
Surface modification of natural zeolites with polymer improves their efficiency and
makes them more selective for adsorption process. Polymer modified with zeolite
forms a bilayer structure on zeolite surfaces. A hybrid polymer has been developed with
silicon alkoxide and a metal alkoxide, a co-monomer. The material is modified by
contact of hybrid polymer with a suspension consisting of zeolite and a solvent. This
modification increases the removal efficiency of the adsorbent (Nemeth and Xu 2014).
Hydrothermal acid-treated faujasite-type zeolites (H-Y14, H-Y40, H-Y144, and
H-Y770) can be modified with two units of polyvinyl alcohols (PVA) with polymeri-
zation degree of 500 (PVA 500) and 2000 (PVA 2000). The zeolite was mixed with a
solution of PVA and stirred. This fabrication results the strong adsorption affinity
toward the organic pollutants (Kawai 2013). The improvements in permeability and
selectivity during gas/liquid separation on introduction of inorganic sieve materials into
an organic polymer matrix have received a worldwide recognition.
In this context, a silane coupling agent ((3-aminopropyl)-diethoxymethylsilane

(APDEMS)) has been used to modify surface of zeolite for mixed matrix membranes
(MMMs). For this, mixture of toluene, APDEMS, and zeolite is stirred under N2.
Afterward the mixture is washed with toluene and methanol to remove the untreated
silane and then dried the modified zeolite under vacuum condition. Other silane
coupling agents are (aminopropyl)-triethoxy silane, N-(aminoethyl)-aminopropyl-
trimethoxy silane, (-glycidyloxypropyl)-trimethoxy silane, and (3- aminopropyl)-
dimethylethoxy silane (Li et al. 2006). The negatively charged surface of zeolite can
be converted into positively charged ions; zeolite is modified with propylamine, and
N- cetyl- N,N,N- trimethyl ammonium brome (CTAB) has also been mentioned in
the literature (Frida et al. 2014).
Modification in Natural Clay
Clays are hydrous aluminosilicate natural adsorbent and are nontoxic to ecosystem.
Clay minerals are classified as chlorite, illite, kaolinite, montmorillonite, smectite,
etc. In which, montmorillonite and kaolinite are widely used because of their low
cost, chemical and mechanical stability, high surface area, and a variety of surface
and structural properties. Natural clays act as a scavenger of pollutants by embracing
cations and anions either through ion exchange or adsorption or both. The clay and
their modified composites have grown to be the materials of increasing interest due
to their nanosized structural and functional properties. Different techniques that have
been used for clay modification are reviewed in this section below.
Polymer-Clay Composites
Polymer-clay composites have received special attention in the field of adsorption. In
minimal addition, it boosts the mechanical, thermal, dimensional, and barrier per-
formance properties of clay material. Several methods have been developed to
fabricate polymer-clay composites (Fig. 5). These are in situ polymerization,
where monomer is dissolved in a solution with clay followed by in situ polymeri-
zation, induced intercalation where polymer or a prepolymer is dissolved in a
solution with clay, and melt processing where polymer is melt-mixed with the clay
above the softening point of the polymer (Gao 2004). Modification of montmoril-
lonite (MMT) with poly (diallyl dimethyl ammonium chloride) (PDADMAC) and
poly-4-vinylpyridine-co-styrene (PVPcoS) has been reported. The surface is modi-
fied by adding the polymer solution to dispersion of MMT (at a volumetric ratio of
2:1) and continually stirred for 1–4 days. After centrifuged and washing to remove
free polymers, the polymers are fabricated over its surface. This modification
increases the affinity of adsorbent to get selective for organic pollutant (Ganigar
et al. 2010). In another study, polyacrylonitrile (PAN) was grafted on kaolinite by
treating kaolinite with different ratios of hexadecylethyldimethylammonium
(HDEDMA) for the sorption of methylene blue and Cr (VI) has also been investi-
gated (El-Zahhar 2015).
a Phase separated b Intercalated c Exfoliated

(Microcomposite) (Nanocomposite) (Nanocomposite)
Fig. 5 Different types of composites arise from interaction between layered silicate and polymers
A variety of polymers including polypropylene, polyethylene, polystyrene,

poly(ethylene oxide), polycaprolactone, polyimides, polyamides, poly(ethylene
terephthalate), polycarbonate, polyurethane, polyethylenimine, and epoxy resins
have been grafted over different types of clay in literatures (Nguyen and Baird
2006; Alsewailem and Aljlil 2013; Bahrami and Mirzaie 2011; Chen et al. 2016;
Zheng and Wilkie 2003). For instance, a natural montmorillonite modified with
polypropylene was prepared by using benzyl tallow dimethyl ammonium salt
composites (at different ratios) by melt mixing and pressing. In this process maleic
anhydride- modified polypropylene was used as a compatibilizer. This process
increases the mechanical, thermal, and dye adsorption capacity of modified clay
(Bahrami and Mirzaie 2011).
Clay Modified with Phosphate

Clays can also be modified with phosphate, where it can be studied for the removal
of heavy metals (Pb, Zn, Cd, Cu, Co, etc.) from aqueous medium that has been
reported. In this view, natural kaolinite clay can be modified by treating with sodium
polyphosphate and monopotassium phosphate (KH2PO4). This modification
increases the ion exchange capacity of clay and, hence, increases the adsorption of
pollutant over surface (Adebowale et al. 2006; Amer et al. 2010; Unuabonah et al.
2007; Olu-Owolabi and Unuabonah 2011). Similarly, montmorillonite and bentonite
modified with KH2PO4 were studied for the removal of heavy metals (Zn, Cu, Co,
Sr, and Cs) (Ma et al. 2011; Unuabonah et al. 2010). Potassium dihydrogen phos-
phate and sodium polyphosphate have also been used for the modification of kaolin.
The phosphate-modified kaolinite clay pretreated with Ca2+ is studied for the
adsorption of Pb2+ from aqueous solution in batch mode. The resulting adsorbent
showed high Pb2+/Ca2+ ion exchange on modified surface (Cojocariu et al. 2012).
Chitosan-Coated Clay
Chitosan-clay nanocomposites have a considerable prospective for the biomedical
field and wastewater treatment. For combining the advantage of this biopolymer
with clay in a drug delivery processes, the hot intercalation technique is used.
It develops quaternized chitosan-montmorillonite (HTCC-MMT) nanocomposite
materials. Glutaraldehyde can also be used for building cross-linking between
chitosan with clay for the release of paracetamol and theophylline and xanthine
and NO-donor compounds (Bothiraja et al. 2014). Chitosan biopolymer-modified
montmorillonite and halloysite have also been reported in the literatures for the
modulation of drugs (Saji George and Luda 2006; Liu et al. 2015a). Similarly,
sepiolite and attapulgite-modified chitosan can also be prepared by acid treatment
with HCl, where acid-treated clay suspension was mixed into the chitosan solution
by stirring. It causes protonation of – NH2 group on chitosan that induces an
expansion of the polymer network and thereby increases the adsorption (Deng
et al. 2012; Elsergany et al. 2016). Eight adsorbents with different chitosan-clay
(bentonite) ratios were prepared by treating chitosan with acid (acetic acid), and then
the dissolved chitosan was mixed with bentonite clay suspension followed by
washing and drying. This modification improved separation and physical character-
istics of adsorbents and increases its selectivity for metal removal (Dey et al. 2016).
Similarly, nano-chitosan kaolin clay was produced in 1 M acetic acid and stabilized
after dropwise addition of mixture of kaolinite and chitosan solution in 3 M NaOH
which are mentioned in literatures. Numerous methods for the modification of
composite materials such as pultrusion, autoclave processing, prepreg method, wet
lay-up, filament winding, template synthesis, fiber placement technology, intercala-
tion of polymer, melt intercalation, in situ polymerization, etc. have also been
reported in the literature (Mazumdar 2001; Dubois 2000; Evans and Pancoski 1989).
Organic Modification of Layered Clay

Organically modified clays are prepared by replacing the exchangeable inorganic
cations present in the natural clay with organic cations of large size. Organic cations
used in replacement process are then able to adsorb other compounds. Organically
modified clay can be prepared by either wet or dry process. In a typical wet process,
unmodified clay slurry is allowed to react with quaternary ammonium compound.
Thereafter, the mixture was filtered, dried, and ground. In dry process, limited
amount of moisture is added to the clay. The clay is then allowed to react
with organic compound in a mixer or pug mill. Finally, the reacted material is
dried and ground (Masooleh et al. 2010). Organically modified montmorillonite
(MMT), bentonite (BN), and commercial Na-BN clay by exchanging hexa-
decyltrimethylammonium bromide (HDTMA) with sodium ions have been tested
for the adsorption of hydrocarbons, phenol, and dyes. The organoclay was prepared
by the dry process in which HDTMA was used as an ammonium source. After
modification, surface properties alter from hydrophilic to hydrophobic, imparting
better interaction of the clay products toward hydrophobic pollutants in the environ-
ment (Binoy et al. 2010; Bedin et al. 2013). In another study, toluene adsorption by
the sodium smectite modified with (HDTMA) by the process of organophilization
has been reported. The technique consisted of organophilization cation exchange of

sodium present in commercial clay, with the quaternary ammonium salt (García-
López et al. 2010). Modification of sepiolite clay was made with a quaternary
ammonium salt, trimethyl-hydrogenated tallow (3MTH) through melt-compounding
approach (Sperberga et al. 2015).
Thermally Activated Clay

Adsorption capacity of an adsorbent is directly related to its physicochemical
properties such as moisture content, volatile matter content, specific surface area,
etc. To improve the adsorption on illite clay surface, it was chemically and thermally
activated by using NaOH and KOH solutions; afterward the material was thermally
activated at 600 C, 700 C, or 800 C temperatures for increase in their mechanical
strength (Egbuna et al. 2014). The thermal activation showed high correlation of the
specific surface area and methylene blue adsorbent value with temperature (Sarikaya
et al. 2000). Thermal activation of calcium bentonite clay at temperature ranges from
100 C to 1300 C has also been reported (Chen and Mah 1997). To increase the
adsorption capacity and specific surface area of kaolinite, thermal treatment at
temperature from 450 C to 650 C has been applied. During this treatment, its
crystalline structure breaks into amorphous and forms one metakaolinite (Hall and
Yalpani 1980).
Chemically Modified Chitosan as Biomaterial
Chitin is the second most abundant natural biopolymer. Chitosan can be produced
chemically from chitin, found in crustaceans and insects. It is a linear cationic
heteropolymer of randomly distributed N-acetylglucosamine (GlcNAc) and glucos-
amine (GlcN) residues with b-1,4-linkage. Its surface is consisting of amino group
and both binary and secondary hydroxyl groups at the C-2, C-3, and C-6 positions,
respectively. Among the other polysaccharides, its chemical structure allows specific
modifications, especially in C-2 position. Being an ideal support material for enzyme
immobilization, chitosan offers an interesting characteristic of nontoxicity, biode-
gradability, biocompatibility, and bioactivity. During modification, the functional
groups allow direct substitution reactions and yield useful materials for different
domains of application. In the following section, different techniques of chitosan
modification are discussed.
Chitosan Modified with Sugar

Improvement in surface potential of chitosan can be made by modification with sugar
moieties for their applications, especially in the field of biomedical science. The first
report on sugar-modified chitosan derivative was published in 1980 by Hall and
Yaplani (Sashiwa and Aiba 2004). They synthesized sugar-bound chitosan by reduc-
tive N-alkylation using NaCNBH3 and unmodified sugar (Sashiwa and Aiba 2004;
Morimoto et al. 2001). Primarily, sugar-modified chitosan had been investigated
mainly for the rheological studies. But now, sugar-modified chitosan can be used
Adsorbent Drug loaded adsorbent

Drug Loading aer washing
Fig. 6 Diagrammatic representation of drug loading in porous adsorbent
for drug targeting because of specific recognition of cells, viruses, and bacteria.
This type of modification has usually been used to introduce cell-specific sugars
into chitosan. Synthesis of sugar-modified chitosan with D- and L-fucose and
their specific binding with lectin and canine polymorphonuclear leukocyte cells
by reductive alkylation were studied. Ulex europaeus agglutinin I (UEA-I) and
N-acetyl-D-glucosamine were used as sugar derivatives, respectively (Park et al.
2003). Chitosan derivative prepared by the covalent attachment of gluconic acid
has also been studied. This sugar-bearing chitosan was further modified by
N-acetylation in alcoholic aqueous solution. This modification improved the
biodegradability of the chitosan (Li et al. 1999). Modification of chitosan by
N-alkylation performed in aqueous methanol with various aldehydes, monosac-
charides, and disaccharides (glycolaldehyde, DL-glyceraldehyde, D-ribose,
D-xylose, D-arabinose, 2-deoxy-D-ribose, D-galactose, 2-deoxy-D-glucose,
3-O-Me-D-glucose, L-rhamnose, L-fucose, GlcNAc) for gene delivery, cell cul-
ture, targeted drug delivery system (Fig. 6), and tissue engineering has also been
studied in the literature (Morimoto et al. 2001; Mourya and Inamdar 2008; Lee
et al. 2005).
Chitosan-Dendrimer Hybrid
Dendrimers are highly branched and symmetrical macromolecule which comes
under polymer family (Zhao and Crooks 1999). Dendrimers are attractive because
of their multifunctional properties (Dong-Lin and Aida 1997; Zimmerman et al.
1996; Shu et al. 2000). The attach-to route and the macromonomer route are the two
main approaches to dendronized polymers (Grayson and Fréchet 2001). In the
attach-to route, the dendrons are attached to the polymers that possess anchor
group (Yin et al. 1998; Jahromi et al. 1998). In macromonomer route, desired
number of dendrons can be attached to the monomer before polymerization.
Most of the chitosan-dendrimer hybrids are synthesized using the attach-to route
approach (Sadeghi-Kiakhani and Safapour 2016). Dendrimers and their derivatives
are commonly used for the dye removal and modification of dyes and textiles
(Sadeghi-Kiakhani et al. 2013a, b, 2015; Mahmoodi et al. 2010). Chitosan-

polypropylene imine dendrimers hybrid (CS-PPI) as a biomordant can be obtained
by firstly treating chitosan with acetic acid and water/methanol mixture. Then, ethyl
acrylate is introduced into the mixture. After stirring at fixed temperature for 10 days,
the solution is quenched and precipitated in acetate saturated with NaHCO3. After
filtration, the filtrate is dispersed in H2O saturated with NaHCO3. Dialyzed against
H2O and lyophilized is done to obtain N-carboxyethyl chitosan ethyl ester. NaOH
solution is added in prepared compound to obtain N-carboxyethyl chitosan. This
modification makes it a highly biocompatible compound (Tsubokawa and Takayama
2000). Similarly, chitosan powder grafted with hyper-branched dendritic polyamide
has also been reported. This modification was achieved by repeating two processes:
(i) addition of methyl acrylate to the surface amino groups and (ii) amidation of
resulting ester with ethylenediamine to give polyamidoamine dendrimer-grafted
chitosan powder (Jianchao and Pu 2012). Other chitosan-dendrimer hybrids that
have been reported mainly include chitosan-polyamide amine, chitosan-poly-
ethylenimine, chitosan-DOBOB acid, chitosan-DOVOB acid hybrid, chiton-poly-
glycerol hybrid, etc. that have also been reported (Sakti 2015). Dendrimerized
magnetic chitosan for the removal of heavy metals has also been mentioned in the
literatures (Buranaboripan 2014).
Cyclodextrin-Linked Chitosan
The cyclomalto-oligosaccharides involve α-, β-, and γ-cyclodextrin (CD), which are
important because of their ability to encapsulate hydrophobic molecules in their
toroidal hydrophobic cavity whose selectivity depends on the number of glucose
units. CD-modified chitosan has applications in various fields including water
treatment (Alamdarnejad et al. 2013), pharmaceuticals, cosmetics, drug delivery
(Wang et al. 2015b), and analytical chemistry. Thiolated carboxymethyl chitosan-
g-cyclodextrin has been prepared by ionic gelation method. In this method,
β-cyclodextrin was grafted onto carboxymethyl chitosan (CMC) in the presence of
1, 6-hexamethylene diisocyanate (HMDI) reagent, which acts as a spacer between
the CD and CMC. Stannous 2-ethylhexanoate catalyst was used to promote reaction
between isocyanate groups of the CMC-HMDI and β-CD. The resulted material is
washed and dried (Wang et al. 2015b; Aoki et al. 2007). Similarly, three different
kinds of CD-modified chitosan beads by ionic gelation method have been studied for
the adsorption of nonionic surfactant 4-nonylphenol ethoxylates (NPEs) (Luzardo-Á
lvarez et al. 2012). In addition, β-CD-modified chitosan has been prepared by
treating with p-toluenesulfonic anhydride. After addition of NH4Cl and HCl, the
resulting product was filtered and dried. This modification increases the hydropho-
bicity, biocompatibility, and enzymatic biodegradability of chitosan and makes
adsorbent a better alternative for hydrophobic drug encapsulation (Buranaboripan
et al. 2014). In another study, the preparation of α-CD and β-CD derivatives by
reductive amination method using 6-deoxy-6-(4-oxobutyramido)-β-CD and
6-oxo-β-CD (Tojima et al. 1998) and mono 2-O-allyl-α-cyclodextrin has also been
discussed in the literatures (Wan et al. 2002).
Chitosan Bound with Crown Ether

Crown ethers have a unique molecular structure and selective coordination ability.
Cross-linking with crown ether imparts properties like tensions of multiple rings
in the molecular structures, active chemical properties, and easy opening of loop
under acid or alkali catalysis (Yuting et al. 2000; Ji et al. 2014). Chitosan and
crown ether form stronger complexing with salt and better selectivity for metal
ions because of the synergistic effect of high molecular weight (Peng et al. 2003).
Two different chitosan-crown ether resins, Schiff base type chitosan-benzo-15-
crown-5 (CTS-B15) and chitosan-benzo-18-crown-6, are synthesized by the reaction
between –NH2 group in chitosan and – CHO in 40 -formyl benzo-crown ether. This
modification increases the adsorption selectivity of chitosan for Pb2+, Cu2+, and
Hg2+ (Yi et al. 2007). Similarly, the chitosan-crown ether cross-link was grafted by
40 -formal benzo-15-crown-5 to obtain cross-linked chitosan with 40 -formal benzo-
15-crown-5(CCTS-N=CH-B-A5-C-5). After grafting it was loaded with palladium
chloride to achieve the heterogeneous catalyst, which can be easily isolated from the
reaction system. This process enhanced its metal ion selectivity (Jenkins and Hudson
2001). In another study, N-benzylidene chitosan (CTB) was synthesized by the
reaction of benzaldehyde with chitosan (CTS). Chitosan-dibenzo-18-crown-6
crown ether (CTSD) and chitosan-dibenzo-18-crown-6 crown ether-bearing Schiff
base group were prepared by the reaction with 4, 40 -dibromodibenzo-18-crown-6
crown ether, respectively. This modification improved the sorption behavior of the
formed chitosan adsorbent (Yuting et al. 2000).
Chemically Grafted Chitosan

Grafting of chitin and chitosan is important for the functionalization and develop-
ment of practically useful derivatives. Ceric ion, Fenton’s reagent, gamma irradia-
tion, ring opening, and various radicals are the various routes of grafting (Nguyen
et al. 2016). Chemically modified chitosan has wide application in the field of
adsorption. For instance, for the biosorption of nickel (II) and phenol from binary
mixtures on glutaraldehyde, cross-linked chitosan beads were grafted with histidine
and Saccharomyces cerevisiae (SC). Glutaraldehyde cross-linked chitosan was
prepared by agitating chitosan beads in glutaraldehyde solution. Immobilization of
histidine (HIS) on the cross-linked chitosan beads (CCBs) resulted as HIS-CCBs
was suspended in phosphate buffer and agitated with NaOH-treated SC powder. This
modification improved the selectivity and adsorption capacity of the adsorbent
material (Nishad et al. 2012). Ion-imprinting technique to prepare cross-linked
metal complexed chitosan in which metal cation acts as a template and regulator
for cross-linking has also been used for decades. Metal ion-imprinted chitosan
material such as Ag+, Ca2+, Cu2+, Fe2+, Ni2+, Pb2+, Cd2+, Hg2+, Cr(VI), Co(II),
etc. has been synthesized to adsorb the corresponding metal ion from aqueous
solution (Shofiyani et al. 2015; Feng et al. 2013; Zhang et al. 2015a; Tang et al.
2013; Liu et al. 2013, 2015b; Ge et al. 2016). For instance, poly(acrylic acid) grafted
and glutaraldehyde cross-linked chitosan nano adsorbent were synthesized by using
Pb2+ as a template ion. The process starts with stirring of chitosan with acrylic acid.
The mixture was heated under a nitrogen stream, and potassium persulfate was
added. After cooling and filtration, the filtrate was again treated with glutaraldehyde.
The treated product was washed several times and dried. HCl was used to remove the
template from the resulted adsorbent material. This modification enhanced the
adsorption properties of produced adsorbent (Sjoholm et al. 2009).
Enzymatic Modification of Chitosan

Modification of chitin and chitosan by enzymatic approach is interesting owing to its
specificity and environmental advantages as compared to chemical modification.
With respect to health and safety, an enzyme offers the potential of eliminating the
hazards associated with reactive reagents. K. H. Sjohlm et al. reported the reductive
amination to hydrophobic modification of chitosan to induce a micellar structure,
and the ability of the modified chitosan to immobilize enzymes has been investi-
gated. Deacetylated chitosan was hydrophobically modified by butyraldehyde (long-
chain aldehyde) via reductive amination. Immobilization is performed by mixing of
glucose oxidase with sodium acetate buffer with chitosan suspension dissolved in
1% acetic acid. Then, reaction mixture consisting of β-D-glucose solution and O-
dianiside was added to the above solution mixture. At last, peroxidase solution in
cold deionized water is added in the solution. This modification increases the
enzyme activity for the adsorbent material (Torres et al. 2012). Enzymatic modifi-
cation of chitosan with quercetin was performed by dissolving chitosan in acetic
acid. After continual stirring, pH was raised to precipitate the modified chitosan.
This solid precipitate was washed by isopropanol. Finally, the modified chitosan was
dried under a vacuum in a phosphorous pentoxide atmosphere. This enzymatic
modification enhanced plasticity, antioxidant, and antimicrobial properties and ther-
mal degradability of the adsorbent material (Kilinç et al. 2002). In another study,
papain was immobilized by cross-linking the enzyme and chitosan by means of
glutaraldehyde. Chitosan treated with acetic acid was precipitated and then washed
with phosphate buffer. After stirring, resulting pellets are resuspended in Buffer
I containing glutaraldehyde. The chitosan-papain conjugate was washed with Buffer
I containing HCl and alone with Buffer I. This modification increases the thermal
stability of the modified adsorbent (Yu et al. 2015). Modification of chitosan with
hydrolytic enzymes such as cellulose (Li et al. 2012a), protease, lipase, pepsin,
chitinase, chitosanase, and lysozymes is also reported in the literature (Yi et al. 2009;
Peng et al. 2015; Dubeau et al. 2011; Zhang et al. 2015b; Salleh et al. 2011).
Agricultural Waste Adsorbents
Agricultural wastes are by-products from the forestry and agricultural sectors. These
waste materials have sufficient potential to be used as a good sorbent because of their
physicochemical characteristics, inexpensive and abundance in nature, and low cost.
The improper disposal of agrowastes can create a serious environmental issue; that is
why the use of these wastes as an adsorbent is an appropriate way to reduce the solid
waste. Agricultural wastes are generally lignocellulosic materials that consist of
three main high-molecular-weight structural components that are lignin, cellulose,
and hemicelluloses. Lignocellulosic materials also contain certain extractive struc-

tural components that have smaller molecular size (Zhu et al. 2016). Agricultural
wastes are better as compared to other industrial waste for development of adsor-
bents because it can be used without or minimum processing (washing, drying,
grinding) and thus reduce production cost. The chemical modification of these
wastes offers several advantages, for instance, it carried out in a single step,
performed at lower temperature, and develops a better porous structure.
Modification Through Acid and Alkali Solutions

The use of agricultural waste as precursor for the production of activated carbon
has increased lately. These adsorbents have commendable removal efficiency for
various organic contaminants through adsorption process. Acidic modification is
applied by different oxidants to increase acidity and the hydrophilic nature the
adsorbent. In this view, the Nigerian waste bamboo (from a petroleum refining
industry) was carbonized and chemically activated with hydrochloric acid. Car-
bonization was done at 400–500 C, and then the material is treated with 0.1 M
HCl and kept in muffle furnace to active the sample. The acid activation increases
the adsorption capacity of adsorbent (Khan et al. 2016). Walnut shells (WNS)
have been chemically modified for the sorption of hydrocarbon (PAH) and fatty
acids (capric acid, lauric acid, palmitic acid, and aleic acid). Surface modification
is achieved via esterification, i.e., conducted in n-hexane with H2SO4 as catalyst.
The – COOH group of fatty acid is esterified with the – OH group of WNS to
form – OCOC group. This reaction changes the surface properties of WNS from
being polar hydrophilic to organophilic. The polarity and aromaticity of the
material induce considerable effect in terms of its adsorption capacity (Khan
Rao and Khatoon 2016). Beside acidic activation, alkali modification could also
be applied to the agrowaste material for surface modification adsorbents. This
modification produces positive surface charges by which it can adsorb the
negatively charged pollutant species. For instance, a plant-based adsorbent
Caryota urens seeds were chemically modified with NaOH. The material was
modified by treating Fenton’s reagent, sodium silicate, and NaOH (Johari et al.
2016). In the literatures, alkali-modified coconut pitch and coconut powder were
reported by using NaOH. This treatment increases the surface roughness, amount
of cellulose exposed on the surface, amount of amorphous cellulose at the
expense of crystalline cellulose, and the removal bonding in the network struc-
tures (Afroze et al. 2016). In another study, for the removal of Zn2+, Eucalyptus
sheathiana bark (agricultural by-product) has been modified with NaOH. To
prepare the adsorbent, bark powder was stirred with NaOH followed by filtration
and washing. The modified product increases the adsorption capacity in aqueous
medium (Ramalingam Subramaniam 2015). Activated carbon from palm oil
fronds and cashew nut shell have been prepared and activated by KOH which
has been reported in the literatures. The procedure followed the carbonation
process at 700 C and then soaked with KOH solution (Water Treatment Using
Carbon Filters: GAC Filter Information 2004; Li et al. 2012b).
Amine-Functionalized Agricultural Waste

The functionalization of lignocellulosic agricultural residues with anime group pro-
vides a mild and eco-friendly alternative as it enhances the binding of functional
group over surface. Raw cassava straw functionalized with epichlorohydrin is used
as an adsorbent material. To prepare the adsorbent, raw material is dispersed in N,
N-dimethylformamide. Aliquot of epichlorohydrin is added in the presence of
pyridine and the reaction product washed with diluted ethanol. Finally, amino
group is introduced into epoxypropyl by-product after reaction with dimethylamine
solution and washed with ethanol. Modification increases the amino group over
surface and composed an effective adsorbent for the sorption of nitrate (Kalaruban
et al. 2016). Similarly, corncob and coconut copra grafted with epichlorohydrin by
the abovementioned method (Kalaruban et al. 2016) have also been reported
(Ezegbirika and Nnaobi 2012). Grafting of amine changed the surface charges
from negative to positive, which is favorable for the nitrate adsorption by electro-
static forces (Ezegbirika and Nnaobi 2012). In another study, fabrication of ground-
nut husk with EDTA has been reported. For this, the powder groundnut husk was
steeped in nitric acid solution and hydrolyzed with sulfuric acid. Finally the mixture
was filtered and the hydrolyzed husk was heated with pyridine and EDTA. The
incorporation of EDTA improved the binding metal ion capacity since it provides the
amino group for exchangeable metal ions (Hena et al. 2015). Modification of
sugarcane bagasse with epichlorohydrin and triethylamine in the presence of
ethylenediamine and N,N-dimethylformamide has been investigated. The reaction
between epichlorohydrin and cellulose was induced after the activation of hydroxyl
group of cellulose molecule, producing hydroxyl cellulose ether. It is then cyclized
by the catalyst to produce epoxy cellulose ether which is used as an intermediate in
the reaction. The modified product was obtained after the grafting reaction between
epoxy cellulose ether and triethylamine. As a result, organic monomers were
embedded in the cellulose skeleton, which resulted in a broad network and increased
the porous structure on the surface of the product (Bayramoglu et al. 2013). The
change in adsorption potential of amine-modified plant biomass of Alyssum caricum
has also been reported. The sorbent, the native biomass, is soaked in NaOH and
filtered and immersed in epichlorohydrin. The resulted mass was washed with
phosphate buffer and grafted with hexamethylenediamine (HMDA). The surface
modification so obtained increases the adsorption of acidic dyes (reactive green
19 and reactive red 19) (Goncalves et al. 2013).
Zinc Chloride-Modified Agrowaste Material

Activation of agricultural waste materials with zinc chloride can be very effective in
adsorbent development. In the literature, activated carbon from coffee husk waste
prepared by chemical activation has been reported. Coffee husk was impregnated
with activating agent ZnCl2, and the activation is carried out in tubular furnace.
Further iron oxide (goethite) was aged in the solution of FeCl3 and NaOH to get
precipitate on the surface of activated carbon. This process dispersed the iron oxide
all over the surface and enhances the catalytic activity (Itodo et al. 2010). In another
study, four substrates, viz., groundnut shell, shea nut shells, poultry wastes, and
poultry dropping-based activated carbon, were chemically activated with ZnCl2 and
H3PO4. In this process, the agrowaste samples were washed and carbonized. After-
ward, these samples were separately mixed with the activating agents and kept into
the ice bath. The activated carbon so generated was washed with HCl (Matichenkov
and Bocharnikova 2001). Tomato-based activated carbon, modified/activated with
Zncl2, has been studied for tetracycline removal. The adsorbent was prepared by
aging the carbonized tomato sorbents with zinc chloride solution. It was observed
that this fabrication improves the pore structure of carbon adsorbent (Salman 2014).
Soil/Silica Adsorbents
Soil, as a natural adsorbent, consists a mixture of minerals, organic matter, gases,

liquids, and various organisms. Soil minerals and organic matter control its physical
and chemical properties (Rosales-Landeros et al. 2013). Important functions of soil
are to provide a growth medium for plants, means of water storage, supply, and
purification. Silica (SiO2) is a very common mineral, and free silica occurs in many
crystalline forms. Its most common form is quartz. Its composition is very close to
pure silicon dioxide: 46.75 w% silicon and 53.25 w% oxygen (Priya 2014). Mod-
ification onto their surface affects their adsorption properties by increasing the
efficiency, sensitivity, and selectivity. Some of modification techniques are discussed
here below.
Modified Soil
Concurrent contamination of soil with organic matter and heavy metals has become
an environmental problem. Through adsorption by soil, these pollutants can be
minimized from their harmful effect by reducing their movement in soil and thus
reduce their potential for plant uptake or groundwater contamination. In the litera-
ture, soil has been modified with sulfuric acid to activate the soil surface for the
removal of textile effluent. This can be prepared by washing, drying, crushing, and
sieving the soil sample. At last, the soil was modified by treating it with sulfuric acid
and stirred for half an hour. This modification due to the presence of aluminosilicates
is anticipated in the color and COD removal and also increases the adsorption
efficiency of the adsorbent (Meng et al. 2009). Lou soil on both layers tillage and
clay was modified with cetyltrimethylammonium bromide (CTMAB), and sodium
dodecylsulphonate to study the adsorption kinetics of phenol has been reported. This
modification increases the adsorption rate of phenol on the surface of adsorbent (She
Xiao-yan et al. 2015). In another study, soft rock addition to sandy soil for phos-
phorous adsorption has also been mentioned (Sharma et al. 2013).
Ligand-Modified Silica Gel

Silica gel is a porous, granular form of silica tetrachloride or substituted chlorosilane/
orthosilicate. Chemical adsorption on silica surface provides immobility, mechanical
stability, and water insolubility. Silica gel surface can be modified by two following
distinct processes: organo-functionalization, in which the modifying agent is an

organic group, and inorgano-functionalization, where the group anchored on the
surface can be organometallic composite or a metal oxide. The most convenient
way to prepare a chemically modified silica gel is achieved by simple immobilization
of the group on the surface by adsorption or electrostatic interaction or other type
of interactions (Priya 2014). In this view, (HBAPE) modified silica gel is prepared
by, firstly, the reaction between the silylating agent (APTES) and the silanol
groups on the surface of silica gel to obtain aminopropylated silica gel (APSG).
After it, functionalization of APSG with HBAPE is performed. This modification
increases the sorption capacity level and selectivity of the sorbent (Das 2010). In another
study, silica gel modified with 4,40 -diaminodiphenylsulfone (DDS)- O-hydroxyben-
zaldehyde (O-HB) is achieved by the reaction of 3-chloropropylsilica gel with DDS.
The product (Si-DDS) is further reacted with (O-HB) to obtain the desired material
(Si-DDS-O-HB) (Radi et al. 2014). Another modification of silica gel doped with
3-aminopropyltrimethoxysilane via 1H-pyrrole-2-carbaldehyde has been reported. The
adsorbent is prepared by mixing of aminopropyltrimethoxysilane into the suspen-
sion of activated silica gel to produce 3-aminopropylsilica. The product so obtained
reacts with pyrrol-2-carbaldehyde to produce the final adsorbent material. This
modification process enhances the sorption of metal ions Cu, Zn, and Cd onto the
surface of adsorbent (Fan et al. 2007). A numerous organic molecules have been
immobilized onto silica surface which include xylenol orange (Akhond et al. 2006),
di(n-propyl) thiuram disulfide (Amarasekara et al. 2009), 4-acylpyrazolone
(Ngeontae et al. 2007), aminothioamidoanthraquinone (Goswami and Sing 2002),
and 1,8-dihydroxyanthraquinone (Ebrahim 2013).
Metal-Organic Framework
Metal-organic frameworks are a class of porous crystalline material that consists of

metal ion clusters and multidentate organic ligands. During the past two decades,
MOFs have shown considerable applications in many areas such as gas storage,
catalysis, gas separation, sensing, light harvesting, and optical luminescence due to
their tunable crystalline hybrid network, high porosity, and rich functionality.
Besides the advantage of their textual properties, modulation of their chemical
properties is also an interesting feature of these materials. After functionalization
the incorporated functional groups improve interaction of material with incoming
molecules. Some of the common approaches used for the MOF modification are
being discussed herein below:
Metal Doping in MOF Structures

The doping of metals in the MOF framework increases the uptake of guest molecules
by providing additional sites for adsorption. For instance, Ce(III)-doped zirconium-
based MOF (UiO) was developed by dissolving zirconium tetrachloride (ZrCl4) and
benzene-1,4-dicarboxylic acid (BDC) in N,N-dimethylformamide (DMF). Then,
CeCl3.7H2O is stirred in DMF and transferred into ZrCl4/BDC solution and stirred.
The reagents are then added with DMF. The system was heated and the product
formed is filtered, washed, and immersed in a dichloromethane solution for solvent
exchange (Lee et al. 2014). In another approach, copper-based MOF doped with
TiO2-carbon nanotube was prepared for sensitization by using layer-by-layer
technique; hole blocking layer-coated fluorine-doped tin oxide (FTO) was dipped
into trimesic acid in DMF solution. Then, acid-functionalized FTO substrate is
dipped into Cu (NO3)2.3H2O in DMF solution followed by washing and drying
(Anbia and Pazoki 2015). Similarly, doping of lithium (Li) in Cu-based MOF was
performed by thermal decomposition in anion species method. In this process,
vacuum-activated copper carboxylate (Cu-BDC) is immersed in LiNO3/ethanol
solution. After filtration, LiNO3-doped Cu-BDC is heated in vacuum for the
removal of nitrate anion and thus obtains Li-doped MIL-53 (Adhikari and Lin
2016). Likewise, MOF-74(Ni) and MOF-74(Co) were post-modified with
Pd-incorporated activated carbon. The carbonation bridge was formed by the
carbonization of sucrose (Botas et al. 2010). Doping of Co, Cu, and Mg into
Zn-based MOF-74 has been prepared by using nitrate salts as metal sources with
2,5-dihydroxybenzene-1,4-dicarboxylic acid (Zhang et al. 2016b). Coumarin-
loaded Zn-MOF-74 was prepared by mixing activated Zn-MOF-74 in a solution
containing n-hexane and coumarin. N-hexane was evaporated and the resulting
material was washed by ethanol and dried under vacuum (Brozek et al. 2015).
Similarly, numerous MOFs doped with other metals like Na, K, Li, Ni, Co, Mg,
etc. have also been reported in the literature (Botas et al. 2010; Mulfort et al. 2009;
Chen et al. 2014).
Functional Groups over MOFs

Post-synthetic modifications of MOFs with functional group while maintaining the
lattice structure have also proven to be a good approach for modification. In this
view, amine functionalization of MOFs has been modified by alkylation with
2-dimethylaminoethyl chloride. This basic amino-functionalized material had
shown significant change in catalytic performances (Gadzikwa et al. 2008). In
another study, azide-functionalized Zn-cornered mixed ligand MOF was formed
by reaction with ethidium bromide monoazide (Ko and Kim 2011). For the
sorption of CO2, four mesoporous UMCM MOFs (1) were post-modified with
acetic, butyric, benzoic, and 4-trifluoromethyl phenyl anhydrides. The materials
were prepared by dissolving synthesized material into the solutions of acetic
anhydride, butyric anhydride, benzoic anhydride, and 4-trifluoromethyl phenyl
anhydrides with chloromethane, respectively. This decoration of functional
groups over resulted product affected the pore environment of the cages and
hence increases the affinity toward sorption (Deng et al. 2010). A multivariate
MOF-5 which contains eight distinct functionalities (-NH 2, -Br, -Cl2, -NO2, -
(CH3)2, -C4H4, -(OC3H5)2, and -(OC7H7)2) in one phase has been reported in
literature. Crystals of MTV-MOFs were obtained by adding Zn(NO 3)2.4H2O to a
N,N-dimethylformamide solution mixture of the acid forms of the selected
organic links (Abid et al. 2013). In another study, alkylamine-functionalized
Zr-MOF and Mg-MOF are prepared by adding the synthesized MOF into the
solution of DMF (Wu et al. 2015; Yang et al. 2016c).
Future Prospects of Modification Techniques
In the recent years, natural adsorbents have proven their appreciable performances
in various areas and industries. Different fabrication approaches reviewed via dif-
ferent functional groups, metal oxides, multidentate compounds, etc. increase effi-
ciency and surface properties of the materials. These natural materials have wide
application in the areas of biomedical science, building constructions, photocatalytic
degradation, gas purification, separation and storage, pharmaceuticals and cos-
metics, solvent vapor recovery, etc., and progressive increase in their applications
is expected. In this view, for the gas transport and storage in the shale matrix, natural
porous clay material has been studied. Gas molecules dynamically adsorb and
desorb simultaneously on the adsorption sites (Mann et al. 2016). Radiation leakage
accident at Fukushima, Japan (2011), calls attention to the awful need of studies for
the durability and effectiveness of emerging materials used for radiation shielding
purpose. As a result, safe storage of nuclear waste materials has become an important
issue, globally. For this, bricks have been produced from the mixture of clay and
borogypsum. This modification increases the comprehensive strength of brick clay
(Eprikashvili et al. 2016). Worldwide agricultural practices demonstrate that among
various agronomical factors, fertilizers are of supreme importance in increasing the
soil fertility and crop yield. In this prospect, combination of natural zeolite
(clinoptilolite) as a natural mineral fertilizer with brown coal as a soil substitute
has been prepared for transferring organic substances in the brown coal into the
matter adorable by plants. This natural material-based fertilizer increases the pro-
ductivity of crops and improved the physical and chemical properties of soil (Zettl
et al. 2015). Similarly, zeolite A4 impregnated with LiCl/MgSO4 and MgCl2/MgSO4
has been developed for open sorption storage process for space heating and hot
water. The impregnation method includes wetting of the zeolite by an aqueous
mineral salt followed by drying (Elsayed et al. 2017). In most of the reported studies
for the adsorption, desalination of silica gel as adsorbent had been used. It suffers
from limited water uptake capabilities leading to a low system performance. To
overcome this problem, CPO-27(Ni) and aluminum fumarate MOFs are commer-
cially available. In the view of their increasing applications in various fields, natural
materials can be considered as a green cleaner and problem-solver.
Cross-References
▶ Environmental Nanotechnology
▶ Role of Bioremediation as a Low-Cost Adsorbent for Excessive Fluoride Removal
in Groundwater
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Advanced Pretreatment Strategies for
Bioenergy Production from Biomass and 62
Biowaste
C. Veluchamy, Ajay S. Kalamdhad, and Brandon H. Gilroyed
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1508
The Composition of Lignocellulosic Biomaterial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1509
Limiting Factors for Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1511
Bioenergy Production by Fermentation and Anaerobic Digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1511
Pretreatment Strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1511
Physical Pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1513
Chemical Pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1517
Biological Pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1520
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1521
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1522
Abstract
Production of biowaste is increasing day by day, due to the abundant availability
of raw materials and their utilities, especially from lignocellulosic-based material
that constitutes 50% of the total biomass around the world. The recalcitrant
structure of lignocellulose material has become resistant for their degradation
C. Veluchamy (*)
Department of Civil Engineering, Indian Institute of Technology Guwahati, Guwahati, India
School of Environmental Science, University of Guelph Ridgetown Campus, Ridgetown,
ON, Canada
A. S. Kalamdhad
Department of Civil Engineering, Indian Institute of Technology Guwahati, Guwahati, India
B. H. Gilroyed
School of Environmental Science, University of Guelph Ridgetown Campus, Ridgetown,
ON, Canada

https://doi.org/10.1007/978-3-319-73645-7_45
1508 C. Veluchamy et al.
and their recovery of valuable material. Many factors like lignin content, crystal-
linity of cellulose, and particle size limit the digestibility of hemicellulose and
cellulose present in the lignocellulose material. To overcome the bottleneck,
several pretreatment strategies have been employed to diminish the rate-limiting
steps. They are generally classified as physical, chemical, and biological pre-
treatment. The physical pretreatments include mechanical (comminution, ultra-
sound, mechanical jet, high-pressure homogenizer), and thermal pretreatments
(liquid hot water, autoclave, electrohydrolysis, microwave oven). The chemical
pretreatments include acid, alkali, organosolv, wet oxidation, and ozonolysis
pretreatment. The biological pretreatments (fungi, microbial consortia, enzyme
pretreatment) or combined pretreatments (thermochemical or alkali thermochem-
ical) are often employed nowadays. This chapter reviews the process description,
mode of action, and challenges of several pretreatments. This chapter also
discusses the future research needs of advanced pretreatment strategies for
bioenergy production from biomaterial.
Keywords
Lignocellulose · Pretreatment strategies · Bioenergy · Limiting factors ·
Biodegradation
Introduction
Increasing global energy demands and the threat of climate change due to green-
house gas (GHG) emissions have flashed the urgent need to develop sustainable and
affordable environmental-friendly energy resources. Worldwide, energy consump-
tion reached 524 QBtu in 2010, and it is estimated to reach 800 QBtu by 2040, with
an average growth rate of 1.5% per year. A large fraction of the world’s total energy
demands, more than 84%, is supported by nonrenewable fossil resources such as
coal, oil, and natural gas. These are not only in limited supply but also cause the
GHG emissions into the atmosphere (EIA 2013). Bioenergy produced from the
renewable feedstocks such as biomass and its associated waste is considered to be
one of the promising alternatives to fossil-derived energy due to several inherent and
significant advantages (Sawatdeenarunat et al. 2015; Veluchamy and Kalamdhad
2017a). Many biodegradable feedstocks, such as wastewater, sewage sludge, food
waste, animal manure, agri-residue, and organic fraction of municipal solid waste,
are used as substrates for bioenergy production. These facilities elucidate the unique
potential for bioremediation and waste stabilization with concurrent bioenergy
production.
In recent years, lignocellulose biomass and its associated waste such as energy
crops and agri-residues have gained much attention as essential feedstocks for the
production of bioenergy and bio-based products (Veluchamy and Kalamdhad
2017e). These lignocellulose feedstocks do not directly compete with the food or
feed production, like conventional biorenewable feedstocks such as sugar and
starch-based crops. In addition to that, high biomass yield even under low inputs
62 Advanced Pretreatment Strategies for Bioenergy Production from. . . 1509
Biogas (CH4+CO2)
Anaerobic
Forest & agri-residues digestion Hydrogen (H2)
Biomass and Pretreatment Sugars
biowaste strategies Ethanol
Fermentation Chemicals
(carboxylicacids,
Energy crops
alcohols, ethers)
Chemicals
Lignin and residues Combustion (syngas,
heat, electricity)
Fig. 1 Overview of integrated biorefinery approach for lignocellulose materials
of energy, water, and fertilizers makes these feedstocks ideal for bioenergy produc-
tion (Sawatdeenarunat et al. 2015). It is expected that the present fossil-based
petrochemical industry gradually will be replaced by biorefineries which produce a
number of valuable products from lignocellulose materials such as gases, alcohols
(fuels), heat, and electricity (Fig. 1).
The Composition of Lignocellulosic Biomaterial
Lignocellulosic biomass is an abundant organic resource with an annual yield of

over 200 billion dry metric tons per year (Kumar et al. 2008). The basic structure of
lignocellulose is comprised primarily of cellulose (35–60%), hemicellulose
(20–35%), and lignin (10–25%) (Zheng et al. 2014) along with smaller quantities
of other organic and nonorganic compounds such as proteins, lipids, and other
extractives (Frigon and Guiot 2010). The carbohydrate components (cellulose and
hemicellulose) are fermentable after hydrolysis, which makes lignocellulosic bio-
mass a suitable feedstock for the bioenergy production. However, the inherent
characteristics of native biomass and its biowaste, such as structural and chemical
properties, make it resistant to biodegradation by enzymes and microbes. Some
commonly used lignocellulosic feedstocks are summarized in Table 1. The amount
of these constituents not only varies within the species but also varies due to growth
conditions and maturation.
Cellulose in a plant consists of parts with a crystalline (organized) structure and
parts with a not well-organized (amorphous) structure. Cellulose, the major constit-
uent of plant cell wall, consists of β-1,4-linked D-glucose units that form linear
polymeric chain of about 8000–12,000 glucose units. Cellulose consists of chains
that are packed together by hydrogen bonds to form highly insoluble structures
called microfibrils (de Vries and Visser 2001).
Table 1 The composition of lignocellulose content in biomass and biowaste

Biomass Cellulose (%) Hemicellulose (%) Lignin (%)
Corn stover 37.5 22.4 17.6
Corn cobs 45.0 35.0 15.0
Wheat straw 38.2 21.2 23.4
Switch grass 31.0–45.0 20.0–31.0 12.0–18.0
Bagasse 38.2 27.1 12.2
Sugarcane 25.0 17.0 12.0
Rice straw 32.0 24.0 13.0
Eucalyptus 38.0–45.0 12.0–13.0 25.0–37.0
Giant reed stalk 33.1 18.5 24.5
Giant reed leaves 20.9 17.7 25.4
Sunflower stalk 31.0 15.6 29.2
Sorghum 22.2 19.4 21.4
Barley straw 37.5 25.3 26.1
Rye straw 38.0 36.9 17.6
Napier grass 45.7 33.7 20.6
Coastal Bermuda grass 25.0 35.7 6.4
Source: Adapted from Sawatdeenarunat et al. (2015)
Hemicellulose, the second most abundant heterogeneous polysaccharides,

consisted by the different units of sugars in the plant cell wall. These are
classified according to the main residue of sugars present in the backbone of
the structural polymer. Xylan, the most abundant hemicellulose polymer, is
composed by β-1,4-linked D-xylose units in the main backbone, which can be
substituted by different side groups such as D-galactose, L-arabinose,
glucuronic acid, acetyl, feruloyl, and p-coumaroyl residues (de Vries and Visser
2001). The other two major hemicelluloses in plant cell wall are galacto(gluco)
mannans, which consist of a backbone of β-1,4-linked D-mannose and
D-glucose residues with D-galactose side chains, and xyloglucans that consist
of a β-1,4-linked D-glucose backbone substituted by D-xylose. The short and
branched chains of hemicelluloses help built a network with cellulose microfi-
brils and interact with lignin, rendering the cellulose-hemicellulose-lignin
matrix extremely rigid.
Lignin is a large and complex aromatic phenolic polymer that confers strength to
the plant cell wall. Lignin is a highly insoluble complex polymer of phenylpropane
units that are joined together by ether and carbon-carbon linkages, forming an
extensive cross-linked network within the plant cell wall. The cross-linking between
the different polymers confers the complexity and rigidity, which is responsible for
the protection of plant cell wall as a whole. In addition to that, it offers protection
against mechanical stress and osmotic lysis, an effective barrier against pathogens.
These properties of lignin make it a more recalcitrant component of the plant cell
wall. The higher the lignin content, the greater the resistance of biomass to chemical
and biological degradation.
Limiting Factors for Biodegradation
Lignocellulose biomass represents a rather unused source for the bioenergy produc-
tion. This is because of many limiting factors such as lignin content, crystallinity of
cellulose, degree of polymerization, moisture content, available surface area, and the
particle size that limit the digestibility of the hemicellulose and cellulose present in
the material (Veluchamy et al. 2017). Decreased particle size with increase in
available surface rather than crystallinity affects the rate and extent of the hydrolysis
stage in biodegradation. Few researchers conclude that the pore size of the substrate
in relation to the particle size of the enzymes is the main limiting factor in the
enzymatic hydrolysis of lignocellulose biomass. Lignin acts as a shield that limits the
rate and extent of enzymatic hydrolysis, preventing the digestible portions of the
substrate to be hydrolyzed (Chang and Holtzapple 2000).
Bioenergy Production by Fermentation and Anaerobic Digestion
The production of bioenergy from lignocellulose material consists of few phases,

namely, pretreatment, anaerobic digestion and fermentation, product separation, and
posttreatment (Fig. 1). A product separation step is not needed for the anaerobic
digestion, because biogas (methane and carbon dioxide) could itself separate from
the digestate liquid fraction under normal condition. The pretreatment is necessary to
improve the rate of production and the total yield of monomeric sugars in hydrolysis
step. Anaerobic digestion is among the most promising bioconversion technologies
for production of renewable bioenergy. However, the production of methane alone
may not sufficiently justify the capital and operating cost associated with a com-
mercial biogas facility. Hence, anaerobic digestion could be integrated into a
biorefinery that facilitates the subsequent breakdown of lignocellulosic biomass
into its constituents: sugars (glucose, galactose, xylose, arabinose, and mannose)
and/or volatile fatty acids (acetic, propionic, butyric, and valeric acids). The pro-
duced monomeric hexoses can be fermented to ethanol easily, while the fermentation
of pentoses is only done by few strains. Volatile products are also not fermented to
ethanol. The solubilized components could be used as precursors for the production
of diverse products ranging from bioenergy (methane, hydrogen), biofuels (ethanol,
methanol, and butanol) (Agler et al. 2011; Rabelo et al. 2011), and organic acids such
as succinic acid (Cherubini 2010).
Pretreatment Strategies
Due to the complexity and variability of lignocellulose biomass chemical structure,

the optimal pretreatment method and its associated conditions depend on the types of
lignocellulose content. Several structural and compositional properties were found to
have impacts on biodegradability. In general, different pretreatment methods such as
physical, chemical, and biological techniques have been proposed as shown in
Fig. 2. However, all methods had a major effect on the accessible area of lignocel-
lulose biomass. In order to improve bioenergy production, an efficient pretreatment
is necessary to disrupt the naturally recalcitrant carbohydrate-lignin shields that
impair the accessibility of enzymes and microbes to cellulose and hemicellulose
(Yang and Wyman 2008; Veluchamy and Kalamdhad 2017d).
The goal of the pretreatment process is to remove lignin and hemicellulose,
reduce the crystallinity of cellulose, and increase the porosity of the lignocellulosic
Fig. 2 The pretreatment strategies applied for the lignocellulose materials

biomass. Pretreatment must meet the following requirements: improve the formation
of sugars or the ability to subsequently form sugars by hydrolysis, avoid the
degradation or loss of carbohydrate, avoid the formation of bioproducts that are
inhibitory to the subsequent hydrolysis and fermentation processes, and be cost-
effective.
Physical Pretreatment
Physical pretreatment does not use the chemicals or microorganisms during the
pretreatment processes. Physical pretreatment is further grouped into mechanical
and thermal pretreatment.
Mechanical Pretreatment
In mechanical pretreatment, the lignocellulose biomass could be comminuted into
smaller piece by numerous mechanisms such as chipping, grinding, and milling.
Mechanical pretreatment is done primarily to disrupt the crystallinity of cellulose
(not applicable for biosludge) by breaking into smaller components resulting in
higher specific surface area and reduced degree of polymerization, thus rendering
the lignocellulose biomass more amenable to succeeding enzymatic hydrolysis. On
the other hand, mechanical pretreatment is energy-intensive and expensive, more-
over time-consuming. Mechanical pretreatment is lesser effective than chemical
pretreatment because it does not remove the lignin content (Zheng et al. 2014).
Moreover, it has been observed that significant restriction in the cellulose accessi-
bility also inhibits the cellulose enzyme. Therefore, mechanical pretreatment method
was used occasionally.
Comminution (Mechanical Ball Mills)

Comminution is a mechanical pretreatment of lignocellulose biomass that can be
applied to reduce the cellulose crystallinity (cutting the lignocellulose biomass into
smaller pieces through a combination of processes such as chipping, grinding, and/or
milling). The comminution of lignocellulose biomass can be accomplished by using
the ball, vibro, hammer, knife, two-rolled, colloid, and attrition mills. The size of the
materials is usually 10–30 mm after chipping and 0.2–2 mm after milling or grinding
(Sun and Cheng 2002). The selection of a comminution machine depends on the
feedstock moisture content. Comminuting dry biomass with moisture contents
ranging from 10% to 15% (wet basis) can be done by two-roll, hammer, attrition,
and knife mills, while colloid mills and extruders are suitable for comminuting wet
materials with moisture content more than 15–20% (wet basis), whereas the ball and
vibro mills can be used for either dry or wet materials (Kratky and Jirout 2011;
Eisenlauer and Teipel 2017). Reduction in particle size can alter the inherent
ultrastructure of lignocellulosic biomass, increase the accessible surface area, and
reduce the degree of polymerization for improved digestibility (Eisenlauer and
Teipel 2017). It was found that vibratory ball milling is more effective than ordinary
ball milling in the case of reducing the crystallinity of cellulose of lignocellulose
materials and improving their digestibility after pretreatment.
High-Pressure Homogenizer
There are a number of pretreatment technologies that incorporate the use of high-
pressure gradients to rupture the cell wall of lignocellulose biomass. As the sample
approaches the impacting rings or collision plates, there is a rapid increase in the
velocity with a decrement in pressure, resulting intense energy release outcomes in
severe turbulence and localized pressure differences that lead to the formation of
cavitation bubbles. As the sample approaches the impacting rings or collision plates,
there is a rapid increase in the velocity with a decrement in pressure. Hence, these
developed forces tear the cell wall and release the cellular cytoplasm in lignocellu-
lose biomass. One of the large-scale studies was conducted, where the municipal
aerobic sludge was disrupted by jetting the sludge to collide with a collusion plate at
30 bar pressure. The homogenization process involves four steps while applying in
the industrial level. The first step is the addition of alkalinity to weaken biomass cell
membranes and to decrease the viscosity. The alkaline biomass (pH 8.5–10) is kept
in a holding tank for a stipulated time. The second step is to mechanically disinte-
grate the biomass floc into relatively fine particles. Then it is homogenized at high
pressure up to 12,000 psi.
Electrohydrolysis (Pulsed-Electric Field)

Electrohydrolysis pretreatment involves application of short burst of high voltage to
a sample placed between the electrodes (Veluchamy et al. 2017). This is also named
as pulsed-electric field pretreatment. The principle of electrohydrolysis pretreatment
relies on electrophoresis, ohmic heating, and electroosmosis resulting in the disin-
tegration of particles and microbial cell lysis (Zhen et al. 2014). The electrophoresis
is the process in which shifting of ions is relative to a static phase depending on its
electrical charge and molecular size (Mahmoud et al. 2010). The process in which
thermal energy is generated by passing electric current through organic materials is
known as ohmic heating (Varghese et al. 2014). The motion of solid particles
suspended in a liquid, under the influence of an electrical field, is known as
electroosmosis (Mahmoud et al. 2010). Electrohydrolysis is the process of passing
direct current (DC) through an ionic substance to solubilize the organic matter by
breaking the bonds between polymers induced by application of current through
electrodes. An electrode when connected to a DC, one electrode becomes a posi-
tively charge and another one becomes a negatively charged electrode. This initiates
the movement of electrolyte toward electrodes, i.e., positive ions move to cathode
and negative ions move to anode.
When an electric field is generated between the parallel plate electrodes, the field
strength (E) is given by E = V/d, where V is the voltage and d is the distance between
two electrodes. Normally in electrohydrolysis pretreatment, the high field strengths
in the range of 5–20 kV/cm are used to significantly rupture the lignocellulose
biomass. When a high-intensity external electric field is applied, a critical electrical
potential is induced in the biomass cell membrane that leads to breakdown and
structural changes of the cell wall of the lignocellulose biomass. This could result in
a dramatic increase in mass permeability and mechanical rupture of the cell wall of
the lignocellulose materials. By applying high-strength electric pulses, this can
create pores in the cell membrane and hence facilitate the entry of acids or enzymes
to break down the holocellulose into its constituent sugars. The advantage of this
pretreatment is that it can be carried out at ambient environment conditions and the
energy usage and its cosumption is low. This is because of the few seconds of pulse
times. This pretreatment can affect the structure of the lignocellulose biomass.
Ultrasonic
Ultrasonic pretreatment is one of the physical pretreatment methods. The reaction
involved in this pretreatment is the rapid collapse and expansion of the micro-
bubbles caused by the localized high-temperature and high-pressure gradient in the
liquid phase that could rupture the cell membrane, releasing the intercellular matter
to the bulk solution. This pretreatment could be accomplished by the exposure to
high-frequency sound waves generated by vibrating probes, commonly known as a
horn. Ultrasonic pretreatment uses the high-intensity ultrasound ranging between
20 and 40 kHz. This pretreatment can disrupt cell wall structure, increase the
specific surface area, and reduce the degree of polymerization, leading to increased
biodegradability of lignocellulose biomass materials. The rupturing of cell wall
occurs when the local pressure in the aqueous phase is reduced below the evapo-
rating pressure, resulting in the formation of gas bubbles. Recently several studies
have been conducted on the use of ultrasound to pretreat the lignocellulose
materials for bioenergy production. This pretreatment could generate monolithic
cavitations that resulted in physical and chemical effects, causing the destruction in
the cell wall structure of lignocellulose biomass. The physical effects are due to the
collapse of cavitation bubbles, which in turn produce an elevated alteration in the
chemical structure through the formation of free radicals (Kumakura and Kaetsu
1983; Saha et al. 2011). The factors such as viscosity, background pressure, solid
content, and solubilized gas concentration can influence the degree of cavitation
produced by sonication pretreatment (Roxburgh et al. 2005). The usage of sonica-
tion pretreatment has been demonstrated in laboratory and in full scale level
treating the municipal wastewater, but limited application for the lignocellulose
biomass.
Thermal Pretreatment
In thermal pretreatment, lignocellulose biomass is rapidly heated by different heating
sources such as hot air, liquid hot water, microwave irradiation, and steam over a
period of stipulated time to encourage the holocellulose hydrolysis with rapid
decompression. The biomass is subjected to temperature in the range of
150–200 C, although lower temperature has also been reported. The pressure
adjoining these temperatures is in the range of 600–2,500 kPa. The major key factors
for thermal pretreatment are the treatment time, exposing temperature, moisture
content, and size of the particle. Thermal pretreatment is highly effective in
increasing the accessible and susceptible surface area of cellulose and enhancing the
degradability of cellulose to microbes and enzymes (Veluchamy and Kalalamdhad
2017; Veluchamy and Kalamdhad 2017c). All studies report a positive impact of
thermal pretreatment on anaerobic digestion.
Liquid Hot Water

This pretreatment is used occasionally throughout the world. This is one of the
hydrothermal pretreatment technologies that does not use chemicals and is used
mostly in industrial level for bioethanol production. This pretreatment uses water at
elevated temperature at high pressures to maintain its liquid form in order to promote
disintegration and separation of lignocellulosic matrix (Negro et al. 2003; Rogalinski
et al. 2008). Temperatures can range from 100 C to 250 C (depending on the type
of sugar formation) and the length of time also ranging from few minutes to an hour
(depending on the amount of sugar formation) (Yu et al. 2010a). This process uses
many of the same features of steam explosion pretreatment, primarily autohydrolysis
without the rapid decompression. This pretreatment is to completely solubilize
hemicellulose and separate it from the rest of the solid material while reducing the
formation of inhibitors. To avoid the formation of inhibitors, the reaction pH should
be kept between 4 and 7 during the pretreatment. Maintaining the pH between this
range could minimize the formation of monosaccharides and degradation products
that can further catalyze hydrolysis of the cellulosic material during pretreatment
(Weil et al. 1997, 1998; Mosier et al. 2005; Veluchamy and Kalamdhad 2017b;
Kohlmann et al. 1995; Mosier et al. 2005a). The generation of reactive cellulose
fibers for the production of pentosans as well as disruption of the entire lignocellu-
lose matrix is achieved through cell penetration of the biomass by water, along with
solubilization of both hemicellulose and lignin by this liquid hot water acting as an
acid (Yu et al. 2010b).
Autoclave (Steam Pretreatment)

During this pretreatment the lignocellulose biomass is pretreated in a vessel and
steam with high temperature (up to 240 C) and pressure for a stipulated time
duration. After a set time, steam in a vessel is released, and the biomass is quickly
cooled down. This pretreatment is to solubilize the hemicellulose to make the
cellulose better accessible for enzymes or microbes and to avoid the formation of
inhibitors. In this process, the in-situ formed acids catalyze the process itself and so
called autoclave steam pretreatment. The role of the formed acids is not to catalyze
the solubilization of hemicellulose but to catalyze the hydrolysis of the soluble
hemicellulose oligomers. The optimal hemicellulose solubilization and hydrolysis
can be achieved by either high temperature and short residence time (270 C, 1 min)
or lower temperature and longer residence time (190 C, 10 min). Depending on the
biomass moisture content, the pretreatment time has been determined. The higher the
moisture content, the longer the pretreatment times and vice versa.
Steam explosion pretreatment is the most commonly used pretreatment method
for the lignocellulosic biomass materials. In this pretreatment, biomass could be
pretreated with a high-pressure saturated steam, at he end of the processes pressure is
suddenly reduced resulted in explosive decompression of the biomass materials. The

pretreatment uses the temperature of 160–260 C (corresponding pressure
0.63–4.83 MPa) for several seconds to a few minutes before the material is exposed
to atmospheric pressure. The biomass in a vessel and a steam mixture is held for a
period of time to promote hemicellulose hydrolysis, and the process is terminated by
an explosive decompression. The rapid flashing to atmospheric pressure and turbu-
lent flow of the material cause fragmentation of biomass material, thereby increasing
the accessible surface area (Cara et al. 2008; Viola et al. 2008) This pretreatment
causes hemicellulose degradation and lignin transformation because of high temper-
ature, thus increasing the potential of cellulose hydrolysis. Lignin is removed only to
a limited extent during this pretreatment, but it is redistributed on the fiber surfaces as
a result of melting and repolymerization/depolymerization reactions (Kabel et al.
2007). The factors such as residence time, temperature, chip size, and the moisture
content could affect the steam explosion pretreatment. The difference between the
steam pretreatment (simple stream) and steam explosion pretreatment (high-pressure
saturated steam) is the quick depressurization and cooling down of the biomass in
simple pretreatment. Whereas in steam explosion pretreatment causes the water in
the biomass to explode at the end of the pretreatment process.
Microwave Oven
Pretreatment through irradiation such as microwave, gamma-ray, and electron beam
radiation has been used to improve the ethanol and biogas production from various
sludge, but little research has been done on the application of them for the lignocel-
lulose biomass. Microwave pretreatment is the most studied irradiation methods. In
this pretreatment, energy is generated by an electromagnetic field and delivered
directly to the material in order to provide rapid heating throughout the material with
reduced thermal gradient. The microwave irradiation and the dielectric response of a
material determine its ability to be heated with microwave energy (Eskicioglu et al.
2007). This pretreatment can more rapidly heat a large volume, reducing the
treatment time that could lead to considerable energy savings. Similar to other
traditional thermal pretreatments, this could have the side effect of producing heat-
induced inhibitors such as phenolic compounds, furfural, and HMF. As a result, it is
important to optimize the pretreatment conditions to avoid the formation of these
inhibitors. Hence, this could not be used individually for lignocellulosic biomass
pretreatment, but it has been used to provide heat for assisting acid or alkaline
pretreatment at relatively low temperatures without compromising the effects. With
the exception of microwave pretreatment, irradiation methods are usually expensive
and have difficulties and challenges in handling large volume, process scaling up,
and unreliable operation in industrial level.
Chemical Pretreatment
Chemical pretreatment refers to the use of chemicals such as acids and bases and the
ionic liquids, to alter the physical structure and chemical characteristics of
lignocellulose biomass. Among the three categorized pretreatments, chemical pre-

treatment is one that received the most recent research interest. Although many
chemical pretreatment methods have been studied for ethanol production, in recent
years it has been applied to biogas production.
Acid Pretreatment
Pretreatment of lignocellulose biomass with acids (dilute or strong aids) at ambient
temperature is done to enhance solubilization of hemicellulose, by this making the
cellulose more easily accessible for the enzymes. The main reaction that occurs
during the pretreatment is the hydrolysis of hemicellulose, especially xylan as
glucomannan that is relatively acid stable. During acid pretreatment, solubilized
hemicellulose could be subjected to hydrolytic reactions producing monomers,
furfural, HMF, and other volatile products in acidic environments (Ramos 2003).
Solubilized lignin will quickly condensate and precipitate in acidic environments
(Liu and Wyman 2003). The solubilization of hemicellulose and precipitation of
solubilized lignin are more pronounced during strong acid pretreatment compared to
dilute acid pretreatment (Hendriks and Zeeman 2009).
The advantage of acid pretreatment is making the cellulose more easily accessible
for the enzymes due to the solubilization of hemicellulose. However, there is some
risk on the formation of volatile degradation products, and this carbon may not be
used efficiently in the ethanol conversion. However, these volatile products can be
converted to methane. Hence, strong acid pretreatment is attractive for methane
production and not for ethanol production, because of the formation of inhibiting
compounds. However, methanogens can handle these compounds like furfural and
HMF to a certain concentration with an acclimatization period. Nevertheless, the
soluble lignin component is risky and often inhibiting for both the processes like
ethanol and methane production.
Alkaline Pretreatment
Alkaline pretreatment uses the bases, such as NaOH, Ca(OH)2 KOH, and NH3.
H2O, to remove lignin and hemicellulose and/or cellulose, rendering lignocellu-
losic biomass more degradable through microbes and enzymes. The reactions
taking place in alkaline pretreatment are solvation (cleavage of lignin-carbohydrate
linkage) and saponification (Tarkow and Feist 1969). This process causes the
biomass to a swollen state and makes the biomass more accessible for enzymes
and bacteria. At strong alkali concentrations, dissolution such as “peeling” of end
groups, alkaline hydrolysis, and decomposition of dissolved polysaccharides can
take place in the lignocellulose biomass. This peeling is an advantage for the later
conversion of lignocellulose biomass to ethanol and methane production. How-
ever, there is a risk on degradation and loss of carbon in the form of carbon dioxide
also increased.
An important aspect of alkali pretreatment is the solubilization, redistribution, and
condensation of lignin and the modification of cellulose crystallinity state. This
pretreatment has a positive effect on the digestibility of cellulose due to the removal
of hemicellulose and part of lignin. However, there is a loss of hemicellulose to
degradation products, and the solubilized lignin components often have an inhibitory
effect. The loss of fermentable sugars and the production of inhibitory compounds
make this pretreatment less effective for the ethanol production than methane
production. This is because methanogens are often capable of adapting these inhib-
itory compounds with particular concentration.
Oxidative Pretreatment
An oxidative pretreatment is one with the addition of oxidative compounds
(hydrogen peroxide (H2O2), peracetic acid, dimethyldioxirane, and peroxymo-
nosulfate) to the lignocellulose biomass that is suspended in water. In most of the
research, the peroxides are transformed in situ into hydroxyl radicals (OH*). The
most simple and frequently used peroxide is H2O2, and few studies were found on
the application of other peroxides for the lignocellulose biomass for the bioenergy
production. Due to this pretreatment, the lignocellulose biomass partially breaks
down lignin and hemicellulose and the release of cellulose fraction for the
enzymes and microbes. This pretreatment is a nonselective oxidation process;
therefore loss of hemicellulose and cellulose could occur. In addition to that,
inhibitors might be generated, due to oxidization of lignin to form the soluble
aromatic compounds (Hendriks and Zeeman 2009). H2O2 is a strong oxidant that
has been used for the lignocellulose biomass pretreatment for both ethanol and
biogas production.
Ammonia Fiber and CO2 Explosion Pretreatment

Ammonia fiber explosion (AFEX) pretreatment is conducted with ammonia loading
around 1:1 ratio (kg ammonia/kg dw biomass) at temperature ranging from ambient
temperature with a duration of 10–60 days or to a temperature of up to 120 C and
high pressure (17–20 bar) for 5–10 min (Alizadeh et al. 2005; Kim and Lee 2005). In
AFEX pretreatment, the lignocellulose biomass is exposed to liquid ammonia at high
temperature and pressure for a period of time, with a subsequent quick reduction of
pressure (Alizadeh et al. 2005). AFEX pretreatment has shown good results on
several lignocellulose biomass such as wood, switch grass, sugarcane bagasse, and
corn stover. The advantages of AFEX, the ammonia could be recovered after
pretreatment, unlike other pretreatments liquid waste fraction has not been formed.
The AFEX pretreatment enables operating at high solid concentration. Recently,
more research interests have started to determine the optimum conditions for the
AFEX pretreatment of lignocellulose biomass.
Carbon dioxide (CO2) explosion pretreatment is conducted with high-pressure
CO2 at high temperature of up to 200 C with a duration of several minutes (Kim
and Hong 2001). The idea behind using CO2 explosion is that it could have lower
temperature than steam explosion and reduced expense compared to AFEX
pretreatment. It was hypothesized that CO2 form carbonic acid when dissolved
in water and this acid increases the hydrolysis rate. CO2 molecules are comparable
in size to water and ammonia, and this could be able to penetrate small accessible
pore size. Due to explosive release of the pressurized CO2, the distribution of
cellulosic structure increases the accessible surface area of the substrate to
hydrolysis (Zheng et al. 1998). Hence, this pretreatment can hydrolyze hemicel-
lulose and cellulose that could be used for conversion of ethanol and methane
production.
Ozonolysis Pretreatment
The reaction taking place in ozonolysis pretreatment, when ozone is applied, this
ozone molecules disintegrate into hydroxyl radicals (OH*) in water, resulting in a
combination of oxidation by both ozone and the (OH*) radicals (Neely 1984). The
pretreatment parameters are the water content in the reactor, particle size, and the
ozone concentration in the gas stream. Among the parameters, water content is the
most important factor affecting the solubilization of lignocellulose feedstocks (Vidal
and Molinier 1988).
The ozonolysis pretreatment is used to degrade lignin and hemicellulose in many
lignocellulosic materials such as wheat straw, bagasse, green hay, peanut, pine cotton
straw, and popular sawdust. Unlike other chemical pretreatments, it does not produce
toxic inhibitory compounds. This pretreatment has an advantage that the reactions
are carried out at room temperature and normal pressure. Furthermore, the ozone can
be easily decomposed by using a catalytic bed or increasing the temperature means
that could be designed to minimize environmental pollution. A drawback of this
pretreatment is that a large amount of ozone is required that could make the process
more expensive.
Organosolv Pretreatment
In recent year, organosolv pretreatment has attracted much attention for utilization of
lignocellulose biomass. In this pretreatment, an organic or aqueous organic solvent
mixture with inorganic acid catalysts (HCL or H2SO4) is used to break the integral
lignin and hemicellulose bounds. The commonly used solvents are the methanol,
ethanol, acetone, ethylene glycol, triethylene glycol, and tetrahydrofurfuryl alcohol
(Thring et al. 1990; Chum et al. 1999). The organic acids such as oxylic,
acetylsalicylic, and salicylic acids could also be used as catalysts in this pre-
treatment. The reaction involved is the simultaneous prehydrolysis by the organic
solvents and the delignification of lignocellulosic biomass.
Biological Pretreatment
Biological pretreatment for enhanced bioenergy production has mainly focused on

fungal microbial consortium and enzymatic pretreatment. Comparing the physical
and chemical pretreatment methods, biological pretreatments usually require lower
energy input, and no chemicals are conducted under much milder environmental
conditions. However, longer pretreatment time has limited the use of these processes
in commercial application (Taherzadeh and Karimi 2008).
Microbial-Consortium Pretreatment
Microbial consortium pretreatment is conducted by the microbes that all screened
from natural environments in rotten lignocellulosic biomass. Microbial pretreatment
has high cellulose and hemicellulose degrading ability with minor affects in lignin
content (Zhang et al. 2011). An approach for applying microbial metabolism to the
challenges of biofuel production involves ensiling, which is commonly used for
enhancing the digestibility of biomass for ruminants. This ensiling process exploits
the capacity of naturally occurring bacteria to ferment the sugars within the ligno-
cellulose biomass and produce the substrate that is more easily digested by ruminal
microorganisms. While these bacterial consortia lack the ability to substantially
degrade the lignin components (Zhong et al. 2011). Moreover ensiling is a relatively
low input process that is anaerobic and therefore does not require mixing and
aeration. For these reasons, ensiling could be incorporated into a biorefinery process
at the earlier stages of energy production.
Fungal Pretreatment
In fungal pretreatment, brown-rot, white-rot, and soft-rot fungi are used to degrade
the lignin and hemicellulose while utilizing little cellulose in lignocellulose mate-
rials. Brown rots mainly attack cellulose, while white- and soft-rot fungi attack both
cellulose and lignin. On comparing these fungi, white-rot fungi are the most effective
for biological pretreatment of lignocellulose materials (Sun and Cheng 2002).
Fungal pretreatment is usually conducted in a sterile environment.
Enzymatic Pretreatment
To increase the bioenergy production from lignocellulose biomass and its biowaste,
enzymes with hydrolytic activity were applied prior to or during the production step.
The most commonly used enzymes are cellulase and hemicellulase. In most of the
cases, the effect of enzymes on bioenergy production was minimal, but the cost of the
enzymes was high; therefore application of enzymatic pretreatment was limited in
commercial application. In general, most of the biological pretreatments are not efficient
as chemical and physical pretreatments. This is because relatively high retention time is
needed in biological pretreatment about 2–5 weeks (Muthangya et al. 2009).
Conclusion
The focus on bioenergy production from the lignocellulose material has attracted a
lot of research, development, and optimization in a number of fields related to
conversion of lignocellulose into biorefinery products. Throughout the world,
more pilot-scale facilities for pretreatments are being constructed, facilitating much
greater evaluation of the technologies, their constraint, and opportunities. The ideal
pretreatment therefore depends on the local conditions such as type, cost of raw
material, and the need of products. The lignocellulose biomass pretreatment and the
intrinsic structure of the biomass itself are primarily responsible for its subsequent
steps. The conditions used in any chosen pretreatment method will affect various
substrate characteristics which in turn govern the susceptibility of the substrate to
subsequent hydrolysis step. Therefore, pretreatment is an extremely important step
in the bioenergy production from the lignocellulosic biomasses. There is a critical
need to understand the fundamentals of various processes that helps in making a
suitable choice depending on feedstock structure. Future research is needed to focus
on development and validation of large-scale systems. In particular handling of
biomass with high solid concentration, large particle size, and varied substrate
from forest and agricultural residues has to be tested and verified to ensure the
long-term stability of a bioenergy production.
Cross-References
▶ Agrowaste Materials as Composites for Biomedical Engineering

▶ An Introduction to Sustainable Materials Management
▶ Biosynthesis and Assemblage of Extracellular Cellulose by Bacteria
Kitchen Wastewater
▶ Potential of Biogas Technology in Achieving the Sustainable Developmental
Goals: A Review Through Case Study in Rural South Africa
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Green Infrastructure: Cost-Effective
Nature-Based Solutions for Safeguarding 63
the Environment and Protecting Human
Health and Well-Being
Daniel Jato-Espino, Luis A. Sañudo-Fontaneda, and

Valerio C. Andrés-Valeri
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1526
Types of Green Infrastructure (GI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1528
Materials Used in Green Infrastructure (GI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1532
Green Roofs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1532
Swales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1533
Grassed Swales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1533
Biofiltration Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1534
Bioswales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1534
Wetlands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1535
Rain Gardens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1536
Permeable Pavement Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1537
Porous Paving . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1538
Interlocking Block Pavers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1539
Grassed Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1540
Benefits of Green Infrastructure (GI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1540
Conclusions and Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1544
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1545
Abstract
Green infrastructure (GI) is a concept that encompasses a set of treatment
technologies aimed at providing an opportunity to reduce the impact of climate
change and urbanization by delivering diverse environmental, social, and
D. Jato-Espino (*) · V. C. Andrés-Valeri

GITECO Research Group, University of Cantabria, Santander, Cantabria, Spain
e-mail: jatod@unican.es; ndresv@unican.es; andresv@unican.es
L. A. Sañudo-Fontaneda
GICONSIME Research Group, University of Oviedo, Mieres, Asturias, Spain
e-mail: sanudoluis@uniovi.es

https://doi.org/10.1007/978-3-319-73645-7_46
1526 D. Jato-Espino et al.
economic benefits, including flood mitigation, water purification, climate adap-

tation, carbon sequestration and storage, enhancement of biodiversity, job crea-
tion, food production, and generation of spaces for recreation. As such, GI can be
a cornerstone of spatial planning strategies intended to restore the health of
ecosystems and improve the quality of life of people through a more livable
and sustainable environment. GI is at the very heart of nature-based solutions
(NBS) policies, which are designed to recover natural processes in cities by
deploying properties inherent to natural ecosystems (ecosystem services). Thus,
GI systems were initially designed and constructed as sustainable drainage
systems (SuDS), also known as Stormwater Best Management Practices
(BMPs), becoming rapidly in multipurpose systems which broadly responded
to the NBS goals of sustainability and resilience. The construction of GI is usually
based in using high-porosity media and vegetation for enhancing water infiltra-
tion, pollutants sequestration, and environmental benefits. Nonstructural GI tech-
niques are normally built up using vegetated surfaces and open-graded aggregate
materials, while structural GI systems rely on high-strength surface materials to
achieve adequate mechanical performance and maintain infiltration and filtration
capacities. Geosynthetics can also be incorporated into GI systems to boost soil
stabilization, as well as water purification and retention.
Keywords
Climate change · Green infrastructure · Materials · Nature-based solutions ·
Sustainable drainage systems · Sustainability
Introduction
The combined effects of urban growth and climate change (CC) are one of the
biggest challenges which humans will have to face in the future as a society, in order
to ensure the sustainability of well-being over time (Hoornweg et al. 2011).
Increased urbanization involves rising amounts of carbon dioxide (CO2) released
to the atmosphere, aggravating the condition of the main human-induced cause
of CC. In fact, about 70% of the world population is forecasted to live in urban
areas by 2050 (Tucci 2001), which highlights the need for taking actions against the
unstoppable environmental harm provoked by human-related activities. Urbaniza-
tion also contributes to exacerbate the two main consequences derived from CC,
such as global warming (GW) and flooding.
On the one hand, the transition from natural to built-up areas entails a reduction in
the amount of vegetated cover, which results in a decrease of both evapotranspiration
and solar reflectance that facilitates the occurrence of the urban heat island (UHI)
effect and, by extension, the warming of cities (Frumkin 2002). Besides, the growth
of global average temperature of 0.76 C experienced from 1850 to 2005 is
also being heightened by CC through the observed increase in greenhouse gases
(Tett et al. 2002). GW can not only result in a decrease of comfort caused by warmer
63 Green Infrastructure: Cost-Effective Nature-Based Solutions for. . . 1527
air but also contribute to creating chemical reactions that favor air pollution and,
therefore, endanger human health.
On the other hand, the increase in the degree of development involves a decrease
in the permeability of the urban skin, which facilitates the rapid generation of runoff
that is conveyed throughout conventional drainage systems, disregarding soil mois-
ture replenishment and groundwater recharge. Furthermore, the severity and fre-
quency of extreme rainfall events are expected to be boosted by CC, which might
exceed the capacity of traditional drainage networks (Huntington 2006). The final
consequence of these considerations is the occurrence of floods, which are likely to
provoke important economic, environmental, and social damage (Tingsanchali
2012). Hence, these phenomena can result in loss of life, harmful impacts on the
environment and human well-being, or deterioration of property.
The concept of green infrastructure (GI) emerged from the alternative designs
taken to deal with the effects of urbanization on drainage. Thus, instead of resorting
to conventional practices consisting of drainage systems that capture water to
minimize runoff and then transfer it to a sewer network formed of a series of pipes
and manholes connected to each other, these designs aimed at reproducing the
natural water cycle (Woods-Ballard et al. 2015). They have been postulated as
measures to attenuate peak flow and control water pollution through infiltration,
transport, and retention means, enhancing the processes of evapotranspiration, water
table recharge, and rainwater reuse (Roy et al. 2008). Fletcher et al. (2015) provided
an extensive overview of the nomenclature proposed over the years to name these
systems, which included GI as one of the most relevant and recurrent terms used for
this purpose, along with the following: Stormwater Best Management Practices
(BMP), integrated urban water management (IWUM), low-impact development
(LID), low-impact urban design and development (LIUDD), stormwater control
measures (SCMs), stormwater quality improvement devices (SQIDs), sustainable
drainage systems (SuDS), sustainable urban drainage systems (SUDS), and water-
sensitive urban design (WSUD).
Traditionally, the benefits provided by these solutions were arranged according to
the called sustainable drainage triangle, which considered water quantity, water
quality, and amenity as the three main fields where the implementation of GI
might make a difference (Woods-Ballard et al. 2007). This triangle was revised to
add a fourth pillar, namely, biodiversity, due to the contribution of GI to creating
attractive habitats for plants and wildlife (Woods-Ballard et al. 2015). The potential
of GI was further extended recently, emphasizing the role these systems can play
regarding other aspects related to urbanization and CC, such as carbon sequestration
and climate adaptation (Charlesworth 2010). This new dimension given to GI is
extremely linked to the concept of nature-based solutions (NBS), which represent
the increasing recognition and consensus that nature is a trigger to provide sustain-
able, cost-effective, viable, and multifunctional solutions to several challenges
(Nesshöver et al. 2017).
GI are categorized as structural or nonstructural measures depending on whether
they are intended to provide certain mechanical properties, such as withstanding
traffic loads, or not. In any case, these systems consist of physical constructions that
can be combined to form treatment trains to improve their performance at different

temporal and spatial scales (Jato Espino 2016). They are usually built using several
layers made of different materials, e.g., open-graded aggregates, vegetation, or
geotextiles, which are responsible for providing the aforementioned features, includ-
ing water retention, pollution sequestration, and social recreation.
Under these premises, the aim of this chapter was to deepen the concept of GI,
providing a description of the main types into which these practices can be divided
and highlighting the potential benefits their implementation can result in according
to the principles of sustainable development. The approach taken to deal with these
aspects focused on the role played by the construction materials used to build GI
systems, whose proper management can make a difference in protecting the envi-
ronment and ensuring human well-being.
Types of Green Infrastructure (GI)
The European Commission for Environment defines GI as “a strategically planned

network of natural and semi-natural areas with other environmental features
designed and managed to deliver a wide range of ecosystem services such as water
purification, air quality, space for recreation and climate mitigation and adaptation”
(EU Commission 2016). This network contains green and blue spaces, with the
former being related to land while the latter reflecting the spaces occupied by water.
This intimate relation between land and water epitomizes the design of GI systems,
becoming an inherent element to classify the different types of GI techniques.
GI influences directly on land-use planning, not only by modifying the water
management paradigm (Morison and Chesterfield 2012) but also by acting as
the foundations of urban retrofitting activities, such as restoration and enhancement
of urban landscape (Kati and Jari 2016). GI, when understood as a useful tool for
planning, becomes fundamental to create and protect urban ecosystems and,
then, turns out to be a better alternative to conventional drainage systems
(Perales-Momparler et al. 2017). There are different ways of naming GI, which
mainly depend upon the country where they are applied (Fletcher et al. 2015). In
order to avoid confusion, an academic research especially tailored to this topic was
carried out, following up from a similar scientific analysis on GI by Sañudo-
Fontaneda et al. (2017b).
GI is very often related to stormwater management, and therefore the most used
terminology is “green stormwater infrastructure” (GSI) (Sañudo-Fontaneda et al.
2017b). Thus, a search combining the keywords green infrastructure and stormwater
was undertaken in the bibliographic database Scopus (Elsevier). The results
amounted to 458 documents divided into 244 scientific articles, 156 conference
papers, 26 reviews, 13 book chapters, and 4 books, among other types of documents
(see Fig. 1). The high number of documents found in a range of 12 years up to
nowadays clearly shows the great impact of GI on stormwater engineering,
highlighting the importance of GI types within the context of stormwater
management.
Fig. 1 Publications
distributed by document type
Fig. 2 Number of publications organized by subject area
Moreover, the subject area where all the documents found were published is key
to define GSI typologies and their main applications. Fig. 2 provides evidence of the
large number of subject areas studying GSI techniques, demonstrating the cross-
cutting and transversal vision of how multidisciplinary and highly impactful on
society GSI is. Environmental science is, by a great distance, the most relevant
subject area. As depicted by Pataki et al. (2011), GI portrays a vital role in coupling
biogeochemical cycles in urban environments through the ecosystem services pro-
vided by GSI. Wendel et al. (2011) also remarked the importance of environmental
science for assessing equitable access to urban spaces by means of GI related to
water infrastructure.
Engineering and social sciences also marked an important status as dominant

subject areas. Engineering covers a rather large area of research mainly based on the
hydrological impact of GSI (Emerson and Traver 2008), monitoring (Mitsova et al.
2011) and designing optimization (Lee et al. 2012). Social sciences have boarded
GSI from a wide range of views, highlighting those related to the improvement of the
livability in cities (Larsen 2015), water scarcity (Coutts et al. 2013) and flooding
management (Zahmatkesh et al. 2015), citizen participation (Mayer et al. 2012),
stormwater governance (Porse 2013), and willingness to implement GSI (Baptiste
et al. 2015), among others.
A high number of publications on GSI have been related to education and urban
planning. Education has been included in many works related to GSI, mainly from
growing greener cities (Vitiello 2008), higher education both at graduate and postgrad-
uate levels (Bradford and Drake 2010; Scott et al. 2014; Ahn 2016), and the application
of a hands-on approach to learn GSI while practicing (Hensley 2014; Price 2015).
The main GSI techniques were identified in the same search within those publica-
tions related to specific practices. Table 1 shows that green, blue, and living roofs have
been the most researched techniques for GSI, representing 21.1% from all the
published research across the world. The high influence of the Green Street Programs
implemented worldwide, especially focused on GSI techniques used to retrofit urban
areas, has had their impact in the results from this study, being undertaken in 19.1% of
the published work (see Table 1). Some of the most utilized GSI techniques within
Green Streets are bioretention cells, rain gardens, and street planters (Sañudo-
Fontaneda et al. 2017b). Other widely used techniques in these programs are perme-
able pavements (17.1%); street trees, tree box planters, and urban forest (7.2%);
bioswales and swales (6.8%); and rain barrels or rainwater harvesting devices (5.6%).
Table 1 Main green Green stormwater infrastructure (GSI) % of

stormwater infrastructure techniques publications
techniques (Source:
Green/blue/living roofs 21.1
Scopus 2000–2017)
Bioretention cells, rain gardens, and street 19.1
planters
Permeable pavements 17.1
Street trees, tree box filter, urban forest 7.2
Bioswales and swales 6.8
Constructed wetlands/urban lakes 6.8
Rain barrels/rainwater harvesting devices 5.6
Filter drains/French drains/infiltration trenches 4.0
Dry and wet ponds/infiltration basins 3.2
Soil bioretention/bioretention column 3.2
Green walls/facades 1.6
Stormwater biofilters 1.6
Stream restoration 1.2
Treatment train 1.2
Floating wetland 0.4
Permeable pavements have probably become the most successful GSI technique
used so far, becoming part of the “superficial skin” of many cities across the
globe, allowing infiltration and recovering the preexisting natural water cycle
before urbanization (Andrés-Valeri et al. 2016). These techniques have had special
repercussion in the design and construction or parking lots, right-of-way drainage,
cycle and pedestrian paths, and low-speed roads in urbanizations (Castro-Fresno
et al. 2013).
Street Trees and Tree Box Planters are part of a greener approach to Sustainable
Drainage (Asawa et al. 2017), being highly utilized in Green Street Programs and
other engineering and architectural Water Sensitive Urban Designs (WSUD)
(Roseen et al. 2009). The main aim of their implementation is the achievement of
the so-called urban forest, where local species of trees are planted back in urban
environments to mimic the hydrological behavior of a natural watershed (McPherson
et al. 2005).
In addition to Green Street approaches, Rainwater Harvesting Systems have
reached a high level of implementation in households and other private and public
properties and buildings, completing a WSUD approach in stormwater management
(Jones and Hunt 2010). These techniques, with special attention to rain barrels, work
as storage devices for stormwater, reducing runoff flows and benefitting this natural
resource by reutilizing water for flushing toilets and gardening (irrigation), among
other demonstrated properties. Furthermore, they play an important role in urban
agriculture, serving as storage tanks for crop irrigation in urban environments
(Smith-Nonini 2016). They can also work as part of bigger treatment train systems
consisting of more GSI, such as permeable pavements or green roofs.
Constructed wetlands and urban lakes consume more surface than those systems
described before. They are commonly designed alongside some urban forest
approaches to generate natural landscapes in urban environments (Xu et al. 2013).
Floating wetland devices are under development over the last years as a new field of
research, becoming inherently linked to constructed wetlands as demonstrated by
Winston et al. (2017) and Schwammberger et al. (2017).
Dry and wet ponds and infiltration basins are also high area consumers and have
been researched under many different perspectives. One of the most holistic
approaches was taken by Abrahams et al. (2017). This approach, called wetland
ecosystem treatment (WET), consisted of the link between permaculture design,
stormwater management to improve flood resilience, biomass production, and bio-
diversity enhancement.
Stream restoration is a field recently incorporated into GSI from a more natural-
ized approach. Stream restoration has been defined by BAE (2017) as a comprehen-
sive process related to physical and biological components, which intends to recover
the structure and function of urban natural streams before disturbance. Bonneau et al.
(2017) also identified the impact of stream restoration on the recovery of the
pre-development conditions of flow regime.
Filter drains, also known as French drains, are a type of GIS with a low number of
research studies undertaken worldwide but a high level of implementation, as
demonstrated by Sañudo-Fontaneda et al. (2017a). Large stretches of highways in
the UK are drainage systems by means of this technique. Filter drains are usually
identified with infiltration trenches; however, there are some differences in the
hydraulic objective pursued by each of them. While infiltration trenches aim to
capture runoff and infiltrate it through them, filter drains are often designed to
capture runoff and convey it toward an infiltration point. Filter drains can also act
as infiltration trenches, but there are some structural differences between them
depending upon their hydraulic aim (Coupe et al. 2016).
Finally, the treatment train scheme represents the combination of several GSI
techniques to achieve even a higher level of water quality purification and water
quantity management (Lashford et al. 2014). Treatment trains are often designed and
constructed in places where high-intensity rainfall regimes are common and con-
ventional drainage systems cannot cope with stormwater, producing flooding events
periodically (Sañudo Fontaneda 2014).
Materials Used in Green Infrastructure (GI)
The construction of GI relies on natural vegetated surfaces, growing media, and

open-graded aggregates. Sometimes, sustainable materials such as recycled or syn-
thetic materials are also included in GI with both functional and aesthetic purposes
(Garg et al. 2017). The design and construction of any GI practice should consider
the physical and chemical characteristics of the study area, including topography,
soil type, depth to water table, and surrounding land use (Charlesworth et al. 2016).
Environmental conditions, construction, and operation constraints and the type and
purpose of the GI practice to be built are other important factors to bear in mind for
selecting suitable materials for the construction of these techniques.
Green Roofs
Green roofs are one of the most extensively used and researched GI technique. The
typical structure of a green roof consists of a vegetated surface coverage, a substrate
or growing media, and a set of permeable layers. A separation geotextile is com-
monly included under the substrate to act as a filtering layer, along with a
geocomposite or lightweight granular bed under the geotextile for draining. Green
roofs also have a thick and strength geofabric installed at their bottom for protecting
the rooftop waterproofing and insulating from the potential injuries caused by the
plants rooting system (Andrés-Valeri et al. 2014a).
Vegetal selection in green roofs is challenging due to the rooftop adverse conditions
for plant survival and growth. Severe droughts, extreme temperatures, high light
intensities, and high wind speeds increase the risk of desiccation and physical damage
to vegetation and substrate (Dvorak and Volder 2010). The composition of roof
vegetation depends on many factors, especially substrate depth conditions. Intensive
green roofs enable installing a wide variety of vegetal species, with the only limitation
of the geometrical, climatic, and structural conditions of the building. In contrast, plant
selection for extensive green roofs is more complex due to substrate depth restrictions.
Suitable plants for extensive green roofs have stress-tolerant characteristics, compact
growth, evergreen foliage, twiggy growth, and drought tolerance (Oberndorfer et al.
2007). Succulent and herbaceous species are one of the most intensively investigated
taxa on green roof sites (Dvorak and Volder 2010), since they are shallow root systems
with the ability of using water efficiently and tolerating extreme conditions on
rooftops. In general, Sedum species have been found to be very reliable for green
roofs, because of their great drought tolerance, with some species surviving up to
4 months without precipitations (Durhman et al. 2006).
Green-roof substrates are composed of a high amount of mineral materials,
including organic matter in the range of 10–15% by weight. The mineral component
may come from different sources and can have different weights depending on the
rooftop load capacity. However, light expanded clay granules and crushed bricks are
two of the most widely used materials with this purpose (Oberndorfer et al. 2007).
Swales
Swales can be successfully built and operated in most soil types. Soils must be
non-compacted to promote adequate root and biological organism developments,
promote water retention for dry periods, and provide filtering and infiltration prop-
erties (Jurries 2003). They must also contain carbon and nutrients to enable initial
vegetation and biota establishment. Soil requirements for swale structures include
clay, sandy, and loam soils. Clay and silt hold moisture adequately, but delay the
downward movement of water and can stop infiltration completely, which makes this
material ideal for berm construction to prevent water flow. Moreover, sandy soils
allow rapid water movement but do not retain it for long-term uses, proving to be
unable to hold water and nutrients and causing their quick drying. Finally, loam soils
consist of a mix of sand, silt, or clay and organic matter (Jurries 2003). These soils
are loose and rich, allowing water infiltration and supporting healthy vegetation
because of their water absorption and moisture storage.
Grassed Swales
Plants are incorporated into swales to favor the deposition of suspended solids
dragging pollutants and contribute to reducing flow rates (Rahman et al. 2011).
Overall, perennial species are preferable to maintain vegetation cover during the
winter season. Vegetal selection depends on the type of swale under construction.
Grassed swales are very easy to construct and do not require large amounts of
materials. Although native grasses are normally recommended for their role in
enhancing biodiversity and wildlife (Charlesworth et al. 2016) using ad hoc designed
grass types, there is room to improve swale performance in terms of both water
quality and quantity (Woods-Ballard et al. 2015). The inclusion of geofabrics and
open-graded aggregates under the growing media demonstrated to be favorable for
reducing suspended solids in grassed swale structures (Andrés-Valeri et al. 2014b).

Swales can be built with bulk materials such as leaves, rotten wood, or straw. A
perforated pipe or other drainage system is often placed below the substrate to help
in conveying runoff without producing overflows during severe storm events.
Concerning the material used to form berms, most recommendations point to low
permeability soils like clay and rocks.
Sometimes, the natural soil under the swale can be waterproofed in order to avoid the
infiltration of conveyed water (Andrés-Valeri et al. 2014b). Geocomposites, bituminous
membranes, and high-density polyethylene (HDPE) coverages are often used with this
purpose. Furthermore, rock and gravel are also used for building up a drainage layer
under the substrate of grassed swales (Andrés-Valeri et al. 2014b) to improve
stormwater quantity management and facilitate the infiltration of conveyed water.
Biofiltration Systems
Bioswales, wetlands, and rain gardens can be classified as bioretention areas, also
called biofilters. Biofiltration systems rely on the use of vegetation to delay runoff
velocities, filter sediment, and pollutant accumulation, guaranteeing water quality
(Ogle and Hoag 2000), as illustrated in Fig. 3. Their structure and performance are
very similar to each other, mainly differing in the floor dimensions of the plants and
their capacity for water treatment.
Bioswales
A bioretention swale or a bioswale is a bioretention system located within the base of

a swale (Fig. 3). Bioswales are vegetated channels designed to treat pollutants
Fig. 3 Bioretention area

derived from stormwater runoff. Stormwater conveyed by sewer networks enters the
channel at the inlet and receives treatment before it leaves through the outlet. In
general, bioswales are at least 30 m long and 0.6 m wide, have a longitudinal slope in
the range from 0.5% to 6%, and are located in series with detention ponds, which
store runoff and reduce peak discharge (Mazer et al. 2001).
Since pollutant reduction is the primary objective of bioswales, a great variety of
vegetal species, including macrophytes, can be used for building the vegetal cover-
age. They should be tolerant to flooding conditions and high organic and inorganic
loadings, as well as adaptable to local weather conditions and diseases (Leroy et al.
2017). The selection and planting of vegetation must be accomplished in accordance
with both the characteristics of the pollutants to be removed and the flow and
velocity design requirements for the bioswale (Jurries 2003). In addition, the vege-
tation selected for a biofiltration swale must have characteristics providing either
vegetal delay of water or Manning’s roughness coefficient between 0.20 and 0.24
(Ogle and Hoag 2000). Choosing between turf or woody plants depends on the
desired capacity and residence time of stormwater and pollutants in the bioswale.
Aboveground plant parts are capable of inducing sedimentation of particulates and
pollutants, while plant roots stabilize sediment deposits, which prevent sediment
re-suspension (Mazer et al. 2001).
Bioswales are generally composed of three basic vegetation zones: high, middle,
and low. Vegetation in the low zone should tolerate standing water and fluctuating
water levels. Plants in the middle zone deal with slightly drier conditions and more
infrequent fluctuating water levels, being often selected for erosion control purposes.
Finally, the high zone can be planted with species adapted for drier conditions.
Woody plant materials should only be located on side slopes, while trees must be
planted along the edge of the bioswale, in order to provide shade to minimize
temperature increases in water during dry months. A lower canopy of shrubs and
grasses can also be planted underneath the trees (Jurries 2003).
Wetlands
Wetlands are frequently constructed by excavating, backfilling, grading, diking, and

installing water control structures to establish hydraulic flow patterns. If the con-
struction site is founded on highly permeable soils, an impervious and compacted
clay liner is usually installed, placing the original soil over the liner. Wetland
vegetation is then planted or allowed to grow naturally (Kadlec and Knight 2004).
A common concern with wetlands is the potential loss of water from infiltration
and contamination of groundwater below the construction site (EPA 1999).
Although there are some applications where infiltration is desirable, the majority
of wetlands require the installation of a barrier to prevent groundwater contamina-
tion. Under ideal conditions, the wetland site consists of natural soils with low
permeability (between 104 and 106 cm/s) that restrict infiltration (EPA 1999;
Winogradoff 2002). If necessary, a barrier can be placed over the natural soil for
preventing excessive infiltration. This barrier is normally built up using clay fills,
bentonite soil layers, chemical treatment of existing soils, asphalt, and synthetic
membrane liners such as polyvinyl chloride (PVC) or HDPE.
Wetland substrates support vegetation and provide sites for both biochemical and
chemical transformations and storage of removed pollutants. Commonly used sub-
strates include soil, sand, gravel, and organic materials (Davis 1995). The soil
substrate for wetland vegetation should be agronomic in nature, well loosened,
and at least 150 mm deep. Depending on the material of the liner, deeper soil
substrates might be required to protect it. Although soils like loam and silt are
suitable for plant growth, they can enable large vegetation mats to float when large
water level fluctuations occur in the wetland. Denser soil substrates such as a sandy
loam or loam gravel mixes can be used to prevent this potential problem.
Constructed wetlands receiving water with high nutrient content, such as domestic
and agricultural wastewaters, can be built with sand or gravel (Davis 1995).
Wetland vegetation is basically composed of six types of vegetal species: free-
floating aquatic species, rooted floating aquatic species, submerged aquatic species,
emergent aquatic species, shrubs, and trees. Plant selection should be carried out using
locally available species, avoiding invasive or aggressive plants, and searching for
tolerance to high pollution loads and continuous flooding. Hence, perennial species
with a slow growth rate and wildlife benefits are normally preferred. The types of
plants that are most often used in constructed wetlands are persistent emergent plants,
such as bulrushes (Scirpus), spikerush (Eleocharis), other sedges (Cyperus), rushes
(Juncus), common reed (Phragmites), and cattails (Typha) (Davis 1995). However,
plant communities in wetlands undergo significant changes with respect to their initial
planting conditions (EPA 1999). Only a few constructed wetlands maintain the
original species composition and density distributions envisioned by their designers.
Rain Gardens
Rain gardens are depressed areas in the landscape designed to manage stormwater
(Dietz 2007). Hence, the aim of rain gardens is to capture and filter stormwater
runoff using a permeable soil substrate and plants tolerant to both drought and
inundation (Richards et al. 2015). Rain garden designs used for stormwater retention
often rely on planted depressions placed downstream from drainage areas. Since
adequate infiltration and percolation rates are essential properties for rain gardens,
careful investigations at potential construction sites must be done. Percolation rate
should be higher than 2.5 cm/h, and organic matter content should be above 5%
(Richards et al. 2017). If the existing soils fail to meet these criteria, they can be
amended by adding sand and compost until obtaining a suitable performance in
relation to those characteristics. High infiltration soils, such as sandy soils, are
recommended for improving rainwater infiltration (Yu et al. 2013). High infiltration
materials like gravel, sand, or plastic cells usually replace underlying soils, in order
to produce draining layers in which perforated pipes are often included for limiting
possible overflows. A geofabric is usually placed over the drainage layer for
avoiding the scouring of fine particles into the drainage outlet.
Perennial native plant species are recommended for rain gardens (Richards et al.
2015), mainly because their capability to develop deep root systems, which enable
building and maintaining high organic matter content and soil porosity. Tradition-
ally, low growing grasses compose the border of the rain garden, while its bottom
consists of a variety of plant species that bloom throughout the growing season. The
selection of these species should consider lower growing native plants whose
eventual height is limited to 1 m. The surface of rain gardens is usually covered
by mulch material, which helps in the erosion control of the soil (Dietz 2007).
Permeable Pavement Systems
In general, neither specific design nor aggregate gradation is used in permeable

pavement systems. The cross section of a permeable pavement cross section consists
of a permeable surface on top, an open-graded bedding layer, a subbase reservoir
layer, and the compacted subgrade. Non-woven geotextiles can also be used to
separate the bedding layer and the reservoir bed and/or to be enable water storage
over the subgrade soil. Perforated pipes, geocomposites, or waterproofing mem-
branes can also be incorporated into the cross section of permeable pavements for
specific applications (Castro-Fresno et al. 2013).
Geotextiles can be used as separation and strengthening layers under roads and
car parks, as well as for filtering purposes in other GI practices. Geotextiles can
enhance organic matter removal by trapping the pollutants deposited on their
surface, enabling microbial biodegradation. Moreover, although geotextiles may
support drainage, their use might lead to potential problems with frost in cold
climatic regions, such as Scotland and Canada (Scholz 2013). The role of geotextiles
is usually divided into five main categories: separation, filtration, drainage, protec-
tion, and reinforcement.
The open-graded bedding layer is normally composed of medium- to small-sized
aggregate materials, usually limestone, in order to provide slightly higher air void
contents than those of the upper layer and prevent stability damages. The subbase
reservoir layer can consist of clean crushed stone with few fine particles, in order to
ensure a minimum void ratio of 40%. Commonly used aggregate materials include
limestone, gravel, basalt, and sandstone (Mullaney and Lucke 2014). Some experiences
concerning the use of recycled or alternative aggregates such as basic oxygen furnace
slag (BOF-slag) in permeable pavements have been reported (Sañudo-Fontaneda et al.
2014). Other options for building the subbase layer of these systems consider plastic cells
(Andrés-Valeri et al. 2014a), which provide the bearing capacity required for withstand-
ing light traffic volumes and ensuring a high storage capacity in the reservoir layer.
There are different types of permeable surfaces that are frequently used in
permeable pavement systems, including porous materials, interlocking block pavers,
and vegetated surfaces reinforced with concrete or plastic grids (Andrés-Valeri et al.
2014a; Rodriguez-Hernandez et al. 2016), as depicted in Fig. 4. Other possible
surfaces include soft paving materials, such as wood mulch and crushed shells,
which are typically used for foot traffic.
Fig. 4 Permeable surfaces. (a) Porous asphalt. (b) Porous concrete. (c) Interlocking block pavers.
(d) Grassed surface
Porous Paving
Porous materials, which are a particular type of surface used in permeable pavement
systems, are made of a granular skeleton coated with a binder. Depending on the
binder used, two main types of porous surface might be defined: porous concrete
(PC), if cementitious material is used as a binder, and porous asphalt (PA), in case the
binder is made of bitumen. PC and PA mixtures are designed to ensure high air void
contents, normally greater than 18–20%, while providing the required bearing
capacity and durability to resist the traffic loads applied during their service life
(Tennis et al. 2004; Alvarez et al. 2011). To guarantee adequate infiltration capac-
ities, open-graded aggregate materials with low or no fine content are used for
building up the granular skeleton (Andrés-Valeri et al. 2016). Aggregates should
ensure angularity, roughness, chemical stability, and an adequate mechanical per-
formance. The criteria for selecting aggregates are normally based on local avail-
ability; however, the most widely used aggregates in PA include limestone, granite,
quartzite, basaltic, and porphyric materials. Although some experiences with
promising results have been also reported in relation to the use of recycled
and synthetic aggregates, further research is needed in this line (Shen et al. 2008;
Frigio et al. 2013).
Binders used for PA mixtures include materials like styrene-butadiene, styrene-

butadiene rubber, crumb rubber, and high-viscosity bitumen (Chen et al. 2013a;
Ibrahim et al. 2014; Rodriguez-Hernandez et al. 2015). Binder content in PA
mixtures is variable, but normally ranges between 5% and 12% by weight,
depending on the binder type, mix design, additives, expected traffic level, and
climatic conditions (Alvarez et al. 2011). The low content of fine particles and the
presence of open-graded aggregates can result in draindown problems for high
bitumen ratios. To prevent this situation, stabilizing fibers are often incorporated
into PA mixtures, including cellulose or mineral materials (Alvarez et al. 2011).
Other materials like Portland cement, hydrated lime, limestone filler, crumb rubber,
or polymeric fibers are also used in PA materials for improving their mechanical
performance, durability, and service life (Alvarez et al. 2006).
Cementitious binders used in PC materials can also vary depending upon the
additives used in the cement paste. Portland cement is the most extensively used
cementitious material for PC mixtures (Tennis et al. 2004), normally in addition to
water reducers, silica fume, viscosity modifiers, and air entraining admixtures (Yang
and Jiang 2003; Andrés-Valeri et al. 2016). Cement content normally exceeds
300 kg/m3 for trafficked applications. Water to cement ratios are generally beyond
0.4 in conventional PC materials, but can be lowered down to 0.2 when additives or
polymeric solutions are incorporated into concrete mixes. These additives are
usually dosed according to manufacturer’s specifications. Interesting developments
have been achieved by adding polymeric solutions to fresh cement paste, resulting in
the so-called polymer-modified porous concrete (PMPC). Various types of poly-
meric additions have been successfully tested in PMPC mixtures, such as styrene-
butadiene polymers, vinyl acetate ethylene (VAE) polymers, acrylic emulsions, or
polyvinyl alcohol formaldehyde solutions (Yang and Jiang 2003; Chen et al. 2013b;
Shen et al. 2013). Among them, VAE polymers have shown the best performance so
far, probably due to their positive chemical interactions with Portland cements.
Interlocking Block Pavers
Permeable interlocking pavers are common pavers, but designed for allowing water
infiltration. Compared with other porous paving materials, properly constructed
block pavements are solid and stable, so that they can bear almost any traffic,
including moving vehicles (Ferguson 2005). They can be divided into two catego-
ries: porous blocks or impervious blocks with open joints. Both systems allow water
to infiltrate across the pavement surface. The air void content in porous materials
normally exceed 20%, while the joints in impermeable blocks cover between 8% and
20% of the total pavement surface area and are usually filled with 2–5 mm aggregate
material (Mullaney and Lucke 2014). This type of surface relies on the geometry of
blocks to provide interlocking and structural strength. Blocks can be used to create a
permeable surface with the aesthetic appeal of brick, stone, or other interlocking
paving materials. Although they are often made with high-strength concrete, there
are also some investigations concerning the use of ceramic pavers.
Porous paving blocks are made of porous concrete reinforced with polymers and
exhibit better fatigue behavior than those without plastics. Still, these improvements
have been found to decrease for low values of stress, to the extent to appear to be
negligible in the case of traffic loads associated with main and highway roads
(Scholz and Grabowiecki 2007). These concrete products can act as pollution
sinks, because of their particle retention capacity during filtration. Hence, the high
porosity of this type of concrete leads to improved infiltration and air exchange
rates. Those pollutants that are filtered out can sometimes be removed by cleaning
the pavement.
Grassed Surfaces
The design and role of grassed surfaces reinforced with plastic or concrete grids
generally have significant differences in relation to the types of surfaces previously
described, especially in terms of the impervious area of the pavement. Grass
reinforced with concrete grids is much larger than individual interlocking block
pavement surfaces, having more open void space to promote infiltration. The
percentage of open voids ranges from 20% to 50% for concrete grids and between
90% and 98% for plastic grids (Mullaney and Lucke 2014).
The materials used for filling the voids in plastic and concrete grids are normally
composed of a suitable combination of mineral aggregates and organic material, in
order to ensure adequate infiltration capacities, sustain vegetation, and filter runoff.
Locally available grasses proving to be resistant to droughts conditions and high
pollutant loads should be selected as vegetal coverage. The grass planted in the gaps
of the paving often experiences severe heat stress in dry periods, which can shorten
their life cycle. In the end, this can erode the soil in the paving apertures during
heavy rainfall. Therefore, this type of system has been reported to be more suitable
for cooler climates (Lucke and Beecham 2011).
Benefits of Green Infrastructure (GI)
The broadening of the concept of GI, whose consideration rapidly evolved from
solutions limited to improve water management to multifunctional systems capable
of responding to a number of additional economic, environmental, and social
challenges, has highlighted the potential positive contribution these techniques
might have to sustainability. An enlightening means to provide evidence of the
role that GI can play in addressing different issues related to the sustainability of
people, planet, and prosperity can be obtained based on the Sustainable Develop-
ment Goals (SDGs). The SDGs are the 17 objectives included in the 2030 Agenda
for Sustainable Development approved in the United Nations Conference on Sus-
tainable Development, held in Rio de Janeiro in 2012 (UN-DESA 2012). A sum-
mary of the SDGs and the targets into which they are divided is given in Table 2.
Table 2 Sustainable SDG Concept Targets

Development Goals
1 No poverty 5
(SDGs) and targets into
which they are divided 2 Zero hunger 8
3 Good health and well-being 13
4 Quality education 10
5 Gender equality 9
6 Clean water and sanitation 8
7 Affordable and clean energy 5
8 Decent work and economic growth 12
9 Industry, innovation and infrastructure 8
10 Reduced inequalities 10
11 Sustainable cities and communities 10
12 Responsible consumption and production 11
13 Climate action 5
14 Life below water 10
15 Life on land 12
16 Peace, justice, and strong institutions 12
17 Partnerships for the goals 19
The description provided about GI techniques, the different types into which they
can be categorized, and the materials that can form them enabled establishing their
relationship to some of the SDGs listed in Table 2. Hence, Table 3 highlights the
specific targets considered by the United Nations in the area of sustainable devel-
opment that can be addressed through the implementation of GI. The materials used
to build GI generally consist of porous media and vegetated surfaces, which provide
a variety of environmental, energetic, and social benefits that can contribute to
achieving up to 28 targets framed in 12 SDGs, as demonstrated in Table 3.
The main original purposes of all GI types were to improve water quantity and
quality management, thanks to the increased porosity of their layers and the pollut-
ants retention and treatment capacity of some materials (Bayon et al. 2015), such as
geotextiles or biochar. These properties strengthen the resilience of urban areas
to flooding phenomena and also reduce the concentration of pollutants in runoff
(Ellis 2013), enabling their future reuse with non-potable purposes and protecting
receiving water bodies. Aspects related to the management of water-related disasters
and the purification of water are considered by the United Nations through SDGs
1, 3, 6, 11, 13, 14, and 15.
The higher solar reflection provided by open-graded and vegetated covers in
comparison with built-up surfaces enables reducing near-surface air temperature
and, therefore, attenuating the effects of global warming. Furthermore, this charac-
teristic also contributes to mitigate the urban heat island effect experienced in urban
areas due to an excessive presence of dark surfaces (Solecki et al. 2005). Conse-
quently, solar reflection plays an important role in increasing resilience to climate-
related hazards expressed in SDGs 1 and 13.
Table 3 Sustainable Development Goals (SDGs) and targets to which green infrastructure (GI)
might contribute
SDG Target
1 By 2030, build the resilience of the poor and those in vulnerable situations and reduce
their exposure and vulnerability to climate-related extreme events [. . .]
2 By 2030, double the agricultural productivity and incomes of small-scale food producers,
in particular women, indigenous peoples, family farmers, pastoralists, and fishers [. . .]
By 2030, [. . .] implement resilient agricultural practices that increase productivity and
production, that help maintain ecosystems, that strengthen capacity for adaptation to
climate change [. . .]
3 By 2020, halve the number of global deaths and injuries from road traffic accidents
By 2030, substantially reduce the number of deaths and illnesses from hazardous
chemicals and air, water, and soil pollution [. . .]
6 By 2030, improve water quality by reducing pollution, eliminating dumping, and
minimizing release of hazardous chemicals and materials, halving the proportion of
untreated wastewater [. . .]
By 2030, substantially increase water-use efficiency across all sectors and ensure
sustainable withdrawals and supply of freshwater to address water scarcity [. . .]
7 By 2030, ensure universal access to affordable, reliable, and modern energy services
By 2030, increase substantially the share of renewable energy in the global energy mix
By 2030, double the global rate of improvement in energy efficiency
By 2030, enhance international cooperation to facilitate access to clean energy research
and technology, including renewable energy, energy efficiency [. . .]
8 Improve progressively, through 2030, global resource efficiency in consumption and
production and endeavor to decouple economic growth from environmental
degradation [. . .]
9 Develop quality, reliable, sustainable, and resilient infrastructure [. . .] to support
economic development and human well-being, with a focus on affordable and equitable
access for all
11 By 2030, ensure access for all to adequate, safe, and affordable housing [. . .]
By 2030, provide access to safe, affordable, accessible, and sustainable transport systems
for all, improving road safety [. . .]
Strengthen efforts to protect and safeguard the world’s cultural and natural heritage
By 2030, significantly reduce the number of deaths and [. . .] people affected and
substantially decrease the direct economic losses [. . .] caused by disasters, including
water-related disasters [. . .]
By 2030, reduce the adverse per capita environmental impact of cities, including by
paying special attention to air quality and municipal and other waste management
By 2030, provide universal access to safe, inclusive, and accessible, green and public
spaces, in particular for women and children, older persons, and persons with disabilities
By 2020, substantially increase the number of cities [. . .] adopting [. . .] integrated
policies and plans toward inclusion, resource efficiency, [. . .] adaptation to climate
change, resilience to disasters [. . .]
12 By 2030, achieve the sustainable management and efficient use of natural resources
By 2020, achieve the environmentally sound management of chemicals and all wastes
throughout their life cycle [. . .] and significantly reduce their release to air, water,
and soil [. . .]
By 2030, substantially reduce waste generation through prevention, reduction, recycling,
and reuse
(continued)
Table 3 (continued)
SDG Target
13 Strengthen resilience and adaptive capacity to climate-related hazards and natural
disasters in all countries
14 By 2025, prevent and significantly reduce marine pollution of all kinds, in particular from
land-based activities, including marine debris and nutrient pollution
15 By 2030, combat desertification, restore degraded land and soil, including land affected
by desertification, drought, and floods, and strive to achieve a land degradation-neutral
world
By 2020, integrate ecosystem and biodiversity values into national and local planning,
development processes, poverty reduction strategies and accounts
In line with the enhanced draining capacity and solar reflectance of GI, permeable
pavements can also have impacts on the safety perception of users, since their
implementation results in both runoff being removed from the surface and increased
visibility for drivers. Therefore, the splash and spray effects produced by runoff
accumulation are decreased, while the reflection of road lights and vehicle headlights
are increased (Rungruangvirojn and Kanitpong 2010). These issues are represented
in SDGs 3, 9, and 11, which concern road safety and traffic accidents reduction.
Those GI practices involving arable vegetated surfaces, such as rain gardens or
green roofs, can help in increasing the amount of cultivated land in urban areas and
improve the socioeconomic progress and well-being of their inhabitants through
enhanced agricultural productivity (Wilkinson and Torpy 2016). This factor
impacted on SDG 2, since the implementation of green arable infrastructures may
provide opportunities to boost the rates of food productivity.
Mitigating carbon dioxide is a great challenge for future societies, since this gas is
the main human-induced cause of climate change and also increases ozone and
particle concentrations (Charlesworth 2010). Vegetation and trees can decrease
ground-level ozone or smog through the attenuation of air temperatures, as well as
absorb particulate matter. Besides, particular GI technologies like green roofs offer
an enhanced behavior in terms of acoustic insulation, providing extra protection
against noise in relation to conventional roofs. As a result, GI might have beneficial
health effects and, therefore, help meeting SDGs 3, 11, and 12.
The presence of GI practices in urban areas also provides an opportunity for
improving energy efficiency, either through its generation from biomass derived
from plant-related surfaces or by reducing its demand in buildings and other urban
spaces using green layers that act as cooling and heating regulators (Saadatian et al.
2013). The objectives established by the United Nations regarding energetic effi-
ciency and facilitated access to energy are included in SDG 7.
The planning and management of landscape patterns must be based on the
presence of natural surfaces, which can act as a trigger for ecological sustainability
(Benedict and McMahon 2012). Furthermore, green urban areas also provide pleas-
ant and comfortable environments for social recreation, while helping to control the
loss of biodiversity produced by the increased degree of development of cities
Table 4 Summary of some of the benefits provided by green infrastructure (GI) reported by
O’Neil (2014)
Dimension Contribution of green infrastructure to sustainable development
Economic 50% of capital costs in relation to traditional drainage solutions
4.5 C of temperature regulation using green roofs and walls
£2.3M of annual contribution of trees through air purification
+40% commercial trading within town centers including green infrastructure
Environmental 9.1% of suspended particles removed by urban vegetation
3.16 kg of carbon stored in 1m2 of green space
3 dB reduction due to the use of grass instead of built-up surfaces
Up to 8 C decrease in urban temperature from vegetated cover
17–20% reduction in runoff using green roofs in residential areas
+50% species transfer when habitats are connected by green areas
Social People happier when living in urban areas covered by large amounts of
green space
83% of respondents believe green areas provide focal points for communities
24% of people more likely to be physically active if have access to green space
40% less chances to be obese if living in a highly green urban area
(Andersson et al. 2014). For these reasons, GI can contribute to fulfilling SDGs
11 and 15 by guarantying the existence of natural inclusive areas and integrating
ecosystem and biodiversity values into planning strategies, respectively.
The construction materials commonly used to build GI, especially aggregates,
polymers, substrate, concrete, or asphalt, can be partially or totally recycled without
compromising their properties and behavior. In addition, these systems can also
contribute indirectly to resource efficiency by protecting from sunlight, atmosphere,
water, and land (Demuzere et al. 2014). These facets of GI are linked to SDGs 8 and
12, which stand for the sustainable management of natural resources, as well as the
recycling and reuse of materials.
As a more tangible proof of the potential benefits of GI to sustainable develop-
ment, Table 4 compiles some facts and figures reported in a series of investigations
and reports related to the impact of green space in urban areas, arranged according to
their economic, environmental, and social contributions.
Conclusions and Recommendations
This chapter explored the concept of green infrastructure (GI) and provided evidence
of their potential efficiency and the main environmental and social benefits they may
induce, with a special focus on the materials commonly used to build them. Based on
the introduction of some relevant terms related to GI, a review about the release of
scientific documents and technical reports related to the use and application of these
techniques was presented to give way to a description of their main types. This task
laid the foundations needed to overview the materials forming different GI practices,
which in turn enabled discussing the positive impacts that these technologies might
have on sustainable development.
The research carried out so far in relation to GI demonstrated that the choice of
materials to build these systems can have a positive influence on a variety of aspects,
including stormwater management, temperature regulation, air purification, and
noise reduction, among others. Overall, suitable plants for vegetated systems should
have a number of characteristics related to stress, pollution, drought, and flooding
tolerance, organic matter content, sediment stabilization, and localness, in order to
avoid invading surrounding ecosystems. Soils to be used as substrate in these
vegetated layers should be loosened to facilitate the growth of microorganisms
and enhance water retention. Regarding the materials used to build open-graded
layers in GI practices, the valorization of plastic cells and alternative aggregates
derived from industrial by-products provides an opportunity to improve both the
bearing and water storage capacities of these systems.
In summary, GI are comprehensive systems capable of mitigating the harmful
effects of two of the greatest threats that humans will have to face over the next
years: climate change and urbanization. Therefore, GI technologies are multi-
functional measures that can make a difference in the achievement of sustainable
development. As such, their implementation should be considered in urban planning
designs and strategies aimed at safeguarding the environment and protecting human
health and well-being.
Cross-References
Acknowledgments The investigation presented in this chapter was possible thanks to the research
project SUPRIS-SUReS (Ref. BIA2015-65240-C2-1-R MINECO/FEDER, UE), financed by the
Spanish Ministry of Economy and Competitiveness with funds from the State General Budget
(PGE) and the European Regional Development Fund (ERDF).
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The Modified Bardenpho Process
64
Ehsan Banayan Esfahani, Fatemeh Asadi Zeidabadi,
Alireza Bazargan, and Gordon McKay
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1553
The Importance of Nitrogen and Phosphorus Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1553
Types of Biological Nutrient Removal Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1556
Advantages of Biological Nutrient Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1558
The History of the Modified Bardenpho Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1559
Biological Phosphorus Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1561
Source of Phosphorus in Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1563
Importance of Phosphorus Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1563
Chemical Removal of Phosphorus: Advantages and Disadvantages . . . . . . . . . . . . . . . . . . . . . . 1564
Biological Phosphorus Removal Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1564
Biological Nitrogen Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1568
Source of Nitrogen in Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1568
Importance of Nitrogen Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1569
Chemical Removal of Nitrogen: Advantages and Disadvantages . . . . . . . . . . . . . . . . . . . . . . . . . 1569
Biological Nitrogen Removal Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1570
Types of Biological Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1573
Suspended Growth Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1574
Attached Growth Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1574
Performance of the Modified Bardenpho Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1578
Reactors in the Modified Bardenpho Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1579
Comparison of the Modified Bardenpho Process with Other BNR Systems . . . . . . . . . . . . . . 1584
Modified Bardenpho Process Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1585
E. Banayan Esfahani · F. Asadi Zeidabadi

Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran, Iran
A. Bazargan (*)
Department of Civil Engineering, K. N. Toosi University of Technology, Tehran, Iran
G. McKay (*)
Division of Sustainable Development, College of Science and Engineering, Hamad Bin Khalifa
University, Qatar Foundation, Doha, Qatar
e-mail: gmckay@hbku.edu.qa

https://doi.org/10.1007/978-3-319-73645-7_87
1552 E. Banayan Esfahani et al.
Nutrient Removal Establishment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1585

COD and Nutrient Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1585
Hydraulic Retention Time (HRT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1586
Sludge Retention Time (SRT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1586
Recycling Ratio (R) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1586
Temperature, pH, and Bubble Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1587
Modified Bardenpho Process Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1587
COD, BOD, TSS, Nutrient, and Heavy Metal Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1587
Viruses Removal in Modified Bardenpho Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1588
Estimation of Greenhous Gas Emissions of Modified Bardenpho Process . . . . . . . . . . . . . . . . 1589
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1590
Abstract
Excess presence of nitrogen and phosphorous, two fundamental prerequisites for
plant photosynthesis, in water can cause noteworthy problems such as eutrophi-
cation and health issues for humans. Hence, efforts have been made to find
solutions decreasing their concentrations. In addition to methods such as ion
exchange, air stripping and breakpoint chlorination for nitrogen removal, and
coagulantion-flocculation for phosphorous removal, biological methods for nutri-
ent removal have also been used. In this chapter the following three categories
will be discussed: nitrogen removal processes, phosphorous removal processes,
and combined nitrogen/phosphorous removal processes. The basic concept of
biological nitrogen removal processes relies on nitrification and denitrification
which are two major steps in the nitrogen cycle. A biological nitrogen removal
process should normally consist of at least one aerobic and one anoxic reactor.
The Modified Ludzack and Ettinger (MLE) process and the Bardenpho process
are two biological nitrogen removal processes. Biological phosphorus removal
(BPR) depends on the incorporation of phosphorus into cell biomass and subse-
quent phosphorus removal by sludge wasting. BPR processes generally consist of
an anaerobic reactor followed by anoxic or aerobic reactors such as the A/O
(anaerobic/aerobic) and PhoStrip processes. Biological combined nitrogen/phos-
phorous removal processes contain all the three main biological conditions
(aerobic, anaerobic and anoxic conditions). The A2/O (anaerobic/anoxic/aerobic)
and the modified Bardenpho processes remove both nitrogen and phosphorous
simultaneously.
The modified Bardenpho process is a biological process which provides
special conditions for both nitrogen and phosphorous removal. This system
consists of five distinct reactors which are respectively: anaerobic reactor, first
anoxic reactor, first aerobic reactor, second anoxic reactor, and second aerobic
reactor. Each reactor provides appropriate conditions to play its special role in the
removal of wastewater impurities. Also, each reactor has specific conditions such
as pH and temperature. The modified Bardenpho process’s performance in the
removal of nitrogen and phosphorous is respectively excellent and good.
Since the modified Bardenpho process has five distinct bioreactors and every
reactor has specific functions and required conditions, there are some critical
64 The Modified Bardenpho Process 1553
parameters in designing the process. These parameters are nutrient removal

establishment, chemical oxygen demand and nutrient ratio, hydraulic retention
time, sludge retention time, recycling ratio, temperature, pH and bubble size.
These parameters play specific roles in the modified Bardenpho process’s effi-
ciency in removing wastewater impurities and should be optimized.
Due to the utilization of five biological stages in the modified Bardenpho
process, not only does the modified Bardenpho process remove nitrogen and
phosphorus efficiently as its main function, but it also has other benefits such as
reducing chemical oxygen demand, biological oxygen demand, total suspended
solids, heavy metals and viruses.
Keywords
Nitrogen · Phosphorous · Biological nutrient removal · Modified bardenpho
process · Optimization
Introduction
The Importance of Nitrogen and Phosphorus Removal
Nitrogen, as the 7th element of the periodic table, and phosphorus, as the 15th
element, are considered as nutrients since they are two fundamental prerequisites for
microorganism growth and plant photosynthesis. However, the excess presence of
these elements in water can cause serious problems; hence, nitrogen and phosphorus
concentration in water are measured and should be limited. In the initial section of
this chapter, some of the most noteworthy problems due to the presence of excess
nutrients in water, namely, eutrophication, health issues for humans, and the increase
of the chemical oxygen demand of the water, will be discussed.
Eutrophication
When the amount of nutrients in the water increases, this is will result by an
overgrowth of plants and algae. Such events are sometimes referred to as algal
blooms. Algal blooms block sunlight from reaching the bottom of the lake or river;
and hence, plants which live in the depths will die due to a lack of energy via
sunlight. The bacterial decomposition of these biomasses will subsequently consume
the oxygen in the water. A decline in the oxygen concentration of the water will
cause hypoxia which impairs the survival of other marine organisms and decreases
water quality (Chislock et al. 2013).
Eutrophication might naturally occur in lakes and rivers through centuries, but
human activities dramatically accelerate the rate of this phenomenon. Human activ-
ity, chiefly pollutants from agriculture, industry, and sewage disposal containing
high amounts of nutrients are the main culprits (Chislock et al. 2013). Eutrophication
can cause serious problems such as damaging drinking water resources, destroying
recreation and aesthetic advantages of lakes and rivers, and causing taste and odor
issues (Dodds et al. 2008). Such problems, in addition to harming the environment,
result in economic losses. Hence, the release of nutrients into bodies of water should
be limited by policies and relevant standards. The total costs, including recreational
water usage, waterfront real state, recovery of endangered species, and drinking
water, have been estimated at approximately $2.2 billion annually as a result of
eutrophication in US freshwaters (Dodds et al. 2008).
The combination of phosphate, nitrogen, and carbon resources causes eutro-
phication, but each has a different impact. A series of experiments which started in
1973 in a small lake (Lake 226 of the Experimental Lakes Area of Northwestern
Ontario) have yielded interesting results. The body of water was separated into
two sections using a sea curtain (Schindler 1974). Both of these two areas
contained the same amounts of nitrogen and carbon, but phosphorus was added
just to the northeast basin of the lake. The investigations illustrated that the main
limiting factor for eutrophication is phosphate since the basin with phosphorus
was covered with microorganisms within 2 months, while the south basin did not
show signs of eutrophication (Schindler 1974). In another experiment in Lake
227, it was demonstrated that a shortage of carbon did not prevent eutrophication
(Schindler 1974).
Due to the catastrophic consequences of eutrophication, various actions have
been taken to combat this phenomenon all around the world. In China, there are over
110,000 lakes, and through the 1990s, most of these lakes faced drastic eutrophica-
tion problems (Liu and Qiu 2007). The main causes of this mishap are rapid
population increase and the disposal of industrial and domestic wastewater into
lakes which cause a dramatic degradation of water quality (Liu and Qiu 2007).
Prevention strategies for confronting eutrophication are divided into two categories:
external and internal nutrient loading control. External methods control point and
nonpoint sources of pollution such as improving sewage treatment systems prior to
discharge into bodies of water, or the inhibition phosphorus detergents and control-
ling the amount of pesticides used in agriculture (Liu and Qiu 2007). Internal
methods consist of sediment dredging, water flushing, and aeration technology to
regulate internal sources of pollution (Liu and Qiu 2007). In addition, planting
aquatic macrophytes such as hyacinth, bulrush, cat’s-tail, and canna is a feasible
method to refine eutrophic lakes. The roots of these plants provide aerobic and
anaerobic conditions for bacterial growth and consequently remove nutrients by
degrading nitrogen and phosphorus compounds (Liu and Qiu 2007). Laws can play a
prominent role in control of water quality and decreasing eutrophication such as the
“Law Concerning Special Measures for Conservation of the Environment of the Seto
Inland Sea” of Japan which has substantially decreased red tides in this country since
the mid-1970s (Imai et al. 2006).
Health Issues for Human

Nitrogen is a basic element of amino acids and protein, and its use in fertilizers has
led to the much needed increase of global food supplies (Wolfe and Patz 2002).
However, if its concentration passes safe thresholds, it will adversely affect terres-
trial, aquatic, and atmospheric domains (Wolfe and Patz 2002; Galloway et al. 2008).
Particularly, nitrogen in the form of nitrite (NO2) and nitrate (NO3) in water can
pose several hazards to human health.
Methemoglobinemia
Methemoglobinemia or blue baby syndrome which is a fatal blood disorder, espe-
cially in infants younger than 6 months, is mainly attributed to high concentrations of
nitrite. Nitrates can also be reduced to nitrites. Nitrite ions oxidize soluble Fe2+ to
insoluble Fe3+ as well as normal hemoglobin to methemoglobin in human blood
(Wolfe and Patz 2002; Nitrate and nitrite in drinking-water 2011). Methemoglobin’s
ability to carry oxygen molecules to the tissues is fundamentally lower than hemo-
globin. According to the severity of a baby’s condition, the infant may develop blue-
gray skin or become lethargic. In extreme cases, methemoglobin concentrations
higher than 50% can cause coma and death (Wolfe and Patz 2002). The normal
methemoglobin level in humans is less than 2%; and in infants under 3 months of
age, it is less than 3% (Nitrate and nitrite in drinking-water 2011).
Carcinogenicity
N-nitroso compounds are mostly carcinogenic compounds which are a result of
nitrite and nitrosatable compounds reacting in the human or animal body (Nitrate
and nitrite in drinking-water 2011). Several investigations about the correlation of
nitrate or/and nitrite and nitrosatable compounds intake and cancer risk have been
published which have concluded that high nitrate concentrations in water have a
positive correlation with increasing gastric and/or esophageal cancer. However, a
number of case-controlled studies have found other conceivable causes for the
cancer (Wolfe and Patz 2002; Nitrate and nitrite in drinking-water 2011). Weyer
et al. (2001) analyzed cancer incidence from 1955 through 1988 in a group of 21,977
Iowa women who were between 55 and 69 years old. Among 3150 cancer inci-
dences, there was no correlation between nitrate concentrations in drinking water
and cancers of the colon, breast, lung, pancreas, or kidney, while there were positive
associations for bladder and ovarian cancers and negative relations for uterine and
rectal cancers (Weyer et al. 2001).
Finally, yet importantly, nitrate like similar anions prohibits iodine uptake and as
a result causes antithyroid effects on the human body (Nitrate and nitrite in drinking-
water 2011). Studies in Slovakia, Bulgaria, Germany, and USA have found a relation
between nitrate intake and thyroid function (Radikova et al. 2008; Hampel et al.
2003; Gatseva and Argirova 2008; Ward et al. 2010); on the other hand, a clinical
study in the Netherlands did not find a correlation between nitrate intake and thyroid
structure or concentration (Hunault et al. 2007; Blount et al. 2009).
Due to the abovementioned hazards of nitrate and nitrite, the United States
Environmental Protection Agency (USEPA) has set the Maximum Contaminated
Level Goal (MCLG) for total nitrate/nitrite at 10 mg/l and for nitrite at 1.0 mg/l (US
Environmental Protection Agency 1996).
Similarly, too much phosphorus concentration can cause health problems such as
kidney damage and osteoporosis. The Wisconsin Department of Natural Resources
(WDNR) has set a phosphorus limit for point sources at 1.0 mg/l (NR 217).
Chemical Oxygen Demand Increase

Chemical Oxygen Demand (COD) is an indicator of wat quality which measures the
amount of oxygen required for the oxidation of all organic substances in water. The
COD of raw municipal wastewater in the United States is about 400 mg/l (can vary
tremendously), phosphorus concentration is 6–10 mg/l, and nitrogen concentration
is about 30–40 mg/l. According to Randall et al. (1998) which takes into account the
growth of new biomass due to photosynthesis, releasing 1 kg of phosphorus into
nature results in 111 kg of biomass with a COD of 138 kg; hence, 6 mg/l phosphorus
produces 828 mg/l COD, more than double the COD of sewage. Also, 1 kg of
nitrogen generates 16 kg of biomass with a COD of 20 kg; so, 30 mg/l of nitrogen in
the untreated sewage is equivalent of 600 mg/l COD, more than the COD of the
organic compound of raw sewage (Randall et al. 1998).
Types of Biological Nutrient Removal Systems
Considering the adverse hazards of nitrogen and phosphorus in water as discussed in

the previous section, efforts have been made to find the best practical, environmental
friendly, and economical solutions to reduce nitrogen and phosphorus concentration,
at least to the levels required by standards. Due to the characteristics of nitrogen and
phosphorus, various chemical and physical methods have been proposed to remove
these nutrients from water. Alternatively, biological methods for nutrient removal
have also been investigated.
There are three major chemical and physical processes for nitrogen removal,
namely, ion exchange, air stripping, and breakpoint chlorination. In the first
method, wastewater flows over an ion exchanger which is very selective to
nitrogen ions (such as ammonium) in the presence of other ions like sodium,
magnesium, and calcium. In this method, either synthetic or natural resins are
utilized as ion exchangers. While natural zeolite clinoptilolite as a microporous
structure of silica and alumina is a natural resin for nitrogen removal from water,
modern ion exchangers are polymer based. In the air striping method, the pH of the
water is increased, with, for example, lime to pH 10.5–11.5, then through an
air-striping tower ammonium is removed from the water and desorbed into the
air by providing enough air and water contact. In the breakpoint chlorination
approach, sufficient amount of free chlorine (via chlorine gas or hypochlorites) is
added to the wastewater in order to remove nitrogen-ammonium from wastewater
by oxidizing it to nitrogen gas. Equation 1 shows the overall equation of this
process.

NHþ þ
4 þ 1:5 HOCL ! 0:5 N2 þ 1:5 H2 O þ 2:5 H þ 1:5 Cl (1)
Chemical and physical removal of phosphorus is fundamentally based on bring-

ing phosphorus out from soluble state, and creating particles by adding coagulants
and flocculants, followed by using solid-liquid separation processes like sedimenta-
tion or filtration for their removal. Aluminum and iron compounds are typical
coagulants for the precipitation of phosphorus from wastewater. In this process,

aluminum and iron compounds react with phosphate in the wastewater and generate
FePO4 and AlPO4 which are highly inclined to sedimentation.
On the other hand, biological processes have major advantages when compared to
physical and chemical methods. Therefore, they will be focused on for the remainder
of the chapter. These processes are divided into three main categories of: nitrogen
removal processes, phosphorus removal processes, and combined nitrogen/phos-
phorus removal processes.
Biological Nitrogen Removal Processes

The basic concept of biological nitrogen removal processes relies on nitrification and
denitrification which are two major steps in the nitrogen cycle. Ammonium is
biologically oxidized to nitrite, and nitrite is oxidized to nitrate in the nitrification
process which is accomplished in aerobic reactors, in which oxygen is the electron
acceptor. In the denitrification process, nitrate is reduced as an electron acceptor in
anoxic reactors to nitrogen gas. Hence, a biological nitrogen removal system should
consist of at least one aerobic and one anoxic reactor. Among the biological nutrient
removal systems, the Ludzack and Ettinger process, the Modified Ludzack and
Ettinger (MLE) process, and the Bardenpho process remove only nitrogen from
wastewater. An oxidation ditch and batch reactor can remove nitrogen, if the amount
of air transferred and the time of different phases are controlled.
Biological Phosphorus Removal Processes

Biological phosphorus removal (BPR) is basically derived from interpolation of
phosphorus into cell biomass and subsequent phosphorus removal by sludge
wasting. Phosphorus accumulating organisms (PAOs) are responsible for phos-
phorus consumption; so, reactors configuration in BPR systems should provide
conditions for PAOs growth. Anaerobic condition in the absence of nitrate and
oxygen is a mandatory first step in BPR systems in which PAOs take in volatile
fatty acids (VFAs) and acetate and produce storage products such as poly-
β-hydroxyal-kanoates (PHA) and polyhydroxybutyrate (PHB). Concurrently,
orthophosphates are released from polyphosphate, and as a result the amount of
phosphorus in the anaerobic condition is increased. The anaerobic condition is
followed by an anoxic or aerobic zone in which storage products are oxidized and
produce energy which is required for new microorganisms to grow. Meanwhile the
dissolved orthophosphate is removed from wastewater and stored in biomass as
polyphosphate. Finally, sludge wasting reduces the phosphorus concentration in
the sewage.
So generally, biological phosphorus removal process consists of an anaerobic
reactor following by anoxic or aerobic reactors. A/O (anaerobic/aerobic) and
PhoStrip processes are two such systems.
Biological Combined Nitrogen/Phosphorus Removal Processes

Biological combined nitrogen/phosphorus removal processes contain all the
three main biological conditions, anaerobic, anoxic, and aerobic conditions.
A2/O (anaerobic/anoxic/aerobic), the modified Bardenpho, and the University of

Cape Town (UCT) processes remove both nitrogen and phosphorus simultaneously.
Although this chapter will provide a general review of all these processes, it will
specifically focus on the modified Bardenpho process.
Advantages of Biological Nutrient Removal
Many chemical and physical methods have been used for nutrient removal in the
past, but biological processes developed simple and practical alternatives for nitro-
gen and phosphorus removal. Each of these methods has its special merits and
demerits. For instance, chemical and physical methods need a high amount of
chemical compounds for nitrogen and phosphorus precipitation; on the other hand,
biological processes require aeration and have a larger land footprint for the various
anaerobic, anoxic, and aerobic reactors. Therefore, after considering the budget, the
desired quality of effluent, the amount of available area for plant construction, and
other aspects, the best and most practical approach should be selected. Nonetheless,
biological processes have found relative popularity in recent years.
During biological nutrient removal processes, nitrogen and phosphorus are
removed from wastewater by utilizing microorganisms in various environmental
conditions; in these processes, the amount of consumable chemical compounds
critically decreases in comparison to chemical and physical methods. For instance,
a small amount of acetate is required during biological phosphorus removal to
improve biomass growth; on the contrary, a lot of aluminum or ferrous salts are
needed for chemical and physical phosphorus removal. The biological nutrient
removal, hence, is a more economical approach. Reduction in the amount of
consumable chemical compound causes substantial decline in excess sludge vol-
umes; hence, biological approaches have both economical and operational benefits.
Furthermore, in most BNR methods, anaerobic and/or anoxic reactors are placed
ahead of aerobic reactors which causes significant reduction in energy consumption
in biological processes in comparison to not only chemical and physical approaches,
but also other conventional biological methods like activated sludge. The presence
of an anaerobic zone decreases the amount of required aeration in the aerobic zone
since aerobic influent has negligible dissolved oxygen and according to mass
transfer equations the oxygen transfer driving force is greater. Also, nitrate as an
electron acceptor in anoxic zones causes COD stabilization.
Biological phosphorus removal systems are the most economical choice for an
effluent standard of 1 mg/l. Adalbert Oneke Tanyi, in a modeling study, illustrated
that biological phosphorus removal can result in concentrations of as low as 0.4,
while for higher phosphorus removal, auxiliary chemical addition is needed
(Tanyi).
Finally, anaerobic and anoxic zones in biological nutrient removal systems
improve the Sludge Volume Index (SVI), a measure of sludge settling properties,
defined as the volume of 1 gram of sludge after settling the aerated liquor for
30 min.
The History of the Modified Bardenpho Process
Nitrification processes were firstly studied in the nineteenth century but were altered
after the invention of the activated sludge method by Arden and Lockett (1914).
Sawyer and Bradney (1945) investigated excess sludge production during their work
on nitrification and denitrification (Sawyer and Bradney 1945). Biological nutrient
removal (BNR) from wastewater developed in the 1960s. Ludzack and Ettinger
(1962) and Wuhrman (1964) evolved biological nitrogen removal systems. Ludzack
and Ettinger’s process utilized biodegradable organic compounds in the influent as a
carbon source for denitrification. Their system consisted of a series of anoxic and
aerobic reactors which were not completely separated; hence, it caused lower control
on wastewater flow between two reactors and also caused different performances in
nitrogen removal. Levin and Shapiro (1965) examined biological phosphorus
removal processes and developed the Phostrip system (Levin and Shapiro 1965).
They illustrated that adding an anaerobic reactor in the wastewater treatment plant
increases polyphosphate storage in microorganisms; so, they utilized an anaerobic
tank in order to release phosphorus. They did not realize the role of carbon source
and orthophosphates, but by adding an anaerobic reactor, they released phosphorus
and used chemical methods and precipitation to remove the phosphorous (Fig. 1).
Simultaneous biological nitrogen and phosphorus removal progresses were
developed in the 1970s predominantly through the work of James Barnard in
South Africa. Barnard (1973) proposed a modification for the Ludzack-Ettinger
system in which he completely separated the anoxic and aerobic zones and returned
a proportion of the wastewater from the aerobic reactor to the anoxic one. With this,
Aeration Tank
Clarifier
Influent
Effluent
Returned Activated
Sludge
Excess
Sludge
Stripper
Tank
Chemical
Sludge Lime Feed
Fig. 1 The Phostrip process, Reproduced with permission from Randall et al. 1998
he successfully removed nitrogen (Barnard 1973). Figure 2 illustrates the Modified

Ludzack-Ettinger process (MLE).
The importance of the anaerobic reactor was firstly realized by Barnard (1974)
who studied previous investigations about biological phosphorus removal with
activated sludge. Subsequently, he used an anaerobic reactor before an aerobic
reactor and designed the Phoredox system which is illustrated in Fig. 3 (Barnard
1974). Fuhs and Chen (1975) proved that this mechanism is biological and not
chemical (Fuhs and Chen 1975).
Barnard developed several biological processes in order to remove nitrogen and
phosphorus separately or together. He devised the 4-stage Bardenpho process in
1973 for biological nitrogen removal which is illustrated in Fig. 4. After that,
Barnard in 1978 added an anaerobic zone before the 4-stage Bardenpho to remove
Recycle flow
Aerobic Tank
Clarifier
Influent
Effluent
Aeration
Anoxic Tank
Returned Excess
Activated Sludge Sludge
Fig. 2 The MLE process, Reproduced with permission from Randall et al. 1998
Aerobic Tank
Anaerobic Tank Clarifier

Influent
Effluent
Aeration
Returned Excess
Fig. 3 The Phoredox process, Reproduced with permission from Randall et al. 1998
Recycle flow
st
1 Aerobic Tank
nd
2 Anoxic Tank nd
Influent 2 Aerobic Tank Clarified
Effluent
st Aeration Aeration
1 Anoxic Tank
Returned Excess
Fig. 4 The 4-stage Bardenpho process, Reproduced with permission from Randall et al. 1998
Recycle flow
st
1 Aerobic Tank
Anaerobic
nd
Tank 2 Anoxic Tank nd
Influen 2 Aerobic Tank Clarified
Effluent
st Aeration Aeration
1 Anoxic Tank
Returned Excess
Fig. 5 The modified Bardenpho process, Reproduced with permission from Randall et al. 1998
phosphorus from wastewater, and as a result, he invented the Modified Bardenpho.

The 5-stage advanced (Modified) Bardenpho is shown in Fig. 5 (Randall et al. 1998).
Marshal Spector (1979) realized that the anaerobic/aerobic configuration of
activated sludge can remove phosphorus and invented the A/O (Anaerobic/Oxic)
system which was similar to the Phoredox system. Also, he added an anoxic zone to
the A/O process in order to remove nitrogen from wastewater. This system is known
as the A2/O (Anaerobic/Anoxic/Oxic) process, and it was identical to a system
configured by Barnard (Fig. 6) (Spector 1979).
Table 1 briefly categorizes the historical development of biological nutrient
removal systems.
Biological Phosphorus Removal
Phosphorus is highly reactive and typically found in the form of PO4 or PO3 in
nature. Phosphorus is a necessary element in the human body since it plays a role in
energy distribution throughout the body as well as in the DNA molecule structure.
Recycle flow
Anaerobic Tank Clarifier

Aerobic Tank
Influent
Effluent
Anoxic Tank Aeration
Returned Excess
Fig. 6 The A2/O process, Reproduced with permission from Randall et al. 1998
Table 1 Historical review of Biological Nutrient Removal (BNR)

No. Year Author(s) Description
1 1914 Arden–Lockett Changes in the nitrification process with the invention of
activated sludge
2 1945 Sawyer–Bradney Investigation of problems of increasing sludge in
nitrification and denitrification
3 1962 Ludzack–Ettinger Using organic biodegradable materials in the inlet flow as
denitrification source (Ludzack-Ettinger process)
4 1964 Wuhrmann Proposing a denitrification step after nitrification, in sludge
systems for nitrification of high-load processes
5 1965 Levin–Shapiro Developing a biological phosphorus removal system known
as PhoStrip by adding an anaerobic reactor in the
wastewater treatment plant
6 1973 Barnard Proposing a modification for the Lufzack-Ettinger system
by separating anoxic and aerobic zones completely and
using an internal recycle (modified Ludzack-Ettinger
(MLE))
7 1974 Barnard Designing the Phoredox system by using an anaerobic
reactor before an aerobic reactor
8 1975 Fuhs–Chen Proving that the Phoredox system is biological and not
chemical
9 1973 Barnard Developing a 4-stage Bardenpho process for nitrogen
removal
10 1978 Barnard Designing a 5-stage Bardenpho process (Modified
Bardenpho) by adding an anaerobic zone as a first stage
ahead of the 4-stage Bardenpho process
11 1979 Marshall Spector Designing a process known as the Anaerobic-Oxic (A/O)
process, which was identical to the Phoredox system
for BPR
12 1979 Marshall Spector Combining the A/O process with an anoxic zone in order to
remove nitrogen (Anaerobic-Anoxic-Oxic (A2/O) process)
Total phosphorus (TP) represents all forms of phosphorus, either dissolved or

particulate. Orthophosphate (e.g., phosphate ion and phosphoric acid) and poly-
phosphates (e.g., pyrophosphate and trimetaphosphate) are soluble in water. The
main difference between these two forms of phosphorus is that polyphosphate
cannot be removed by precipitation with metal salts and it must first be changed to
orthophosphates with biological activity (Moore 2010). The third form of phos-
phorus is organic phosphorus which is either dissolved or suspended in water.
Particulate organic phosphorus can be removed by precipitation. Dissolved organic
phosphorus is divided into biodegradable and nonbiodegradable, and the biode-
gradable portion can be converted to organophosphate with biological processes
(Moore 2010).
Unlike nitrogen or other compounds, the phosphorus cycle is limited in terres-
trial and aquatic environments. Phosphorus is not naturally found in the gaseous
state. Hence, phosphorus slowly cycles between the water, soil, and sediments.
Phosphorus is typically in the form of phosphate salts in the soil or marine
sediments, and it is a limiting factor for plant growth. Phosphorus is taken up
from sediments by plants, then moves to animals’ bodies through eating, and
finally, when plants or animals dye or urinate/defecate, the phosphorus moves to
the soil or marine sediments again. Human activities like utilizing fertilizers can
disturb this cycle.
Source of Phosphorus in Wastewater
There is a wide variety of phosphorus sources in the wastewater. Domestic waste-

water, especially in region with high detergent and cleaning products, is one of the
main point sources of phosphorus. Also, septic tank wastewater disposal system is
another possible source of phosphorus (Lee et al. 1978). Industrial and municipal
wastewater are point sources of phosphorus. Protein-rich foods such as meat, nuts,
beans, milk and soya have high amounts of phosphorus and consequently wastewa-
ters from these industries have high concentration of phosphorus. Drainage from
agricultural and urban lands, livestock’s excreta and atmospheric deposition are
nonpoint sources of phosphorus which can increase this nutrient amount in the
wastewater (Lee et al. 1978).
Importance of Phosphorus Removal
Any added phosphate is almost immediately uptaken by plants, and only small
amounts can cause exponential growth in plants. Phosphorus concentration in
water in more critical since cyanobacteria (blooms of cyanobacteria and eukaryotic
algae cause eutrophication) are capable of absorbing their required nitrogen from
fixation of atmospheric nitrogen (N2) (Seviour et al. 2003); so, as mentioned in
section “The Importance of Nitrogen and Phosphorus Removal,” phosphorus is the
main cause of algal blooms in the aquatic environment.
Chemical Removal of Phosphorus: Advantages and Disadvantages
Chemical and physical processes in wastewater treatment rely on chemical and

physical properties of elements such as reactivity, density, and mass transfer. Chem-
ical processes for phosphorus removal are based on phosphorus reactions with for
instance lime or metal salts (e.g., aluminum or iron). Aluminum salts, ferric salts, and
lime react with the phosphate and form AlPO4, FePO4 and Ca5OH(PO4)3 which
precipitate in water and consequently remove the phosphate from water. Aluminum
sulfate (Al2(SO4)3) and ferric chloride (FeCl3) are widely used in comparison to
other aluminum and iron salts.
Chemical removal of phosphorus is a common undertaking in wastewater treat-
ment plants (WWTP) which is implemented either alone or with biological processes
to reduce costs and sludge production. Chemical methods provide higher phospho-
rus removal efficiency by consuming more chemical compounds. Also, chemical
phosphorus removal has a lower sensitivity to environmental conditions such as
temperature and wastewater influent composition in comparison to biological pro-
cesses. These methods, however, are costly and produce more sludge, and they
increase water salinity with unwanted by-product salts.
Biological Phosphorus Removal Process
Enhanced biological phosphorus removal (EBPR) systems remove phosphorus

economically, microbiologically, and in an environmentally friendly manner. Such
systems are historically designed by putting an anaerobic zone ahead of anoxic and
aerobic zones. For example, if an anaerobic zone is placed upstream of the MLE and
Bardenpho processes which only remove nitrogen biologically, the resulting 3-stage
Phoredox and Modified Bardenpho processes remove phosphorus as well (Seviour
et al. 2003). It is generally believed that in the anaerobic zone, PAOs assimilate
VFAs and convert it to PHA and also synthesize acetate to PHB which are stored in
PAOs structure as an energy and carbon source for the subsequent steps. Meanwhile,
polyphosphates are hydrolyzed to orthophosphates, and phosphorus concentration in
the anaerobic zone is substantially increased. Figure 7 schematically shows this
process in the anaerobic reactors.
In the following aerobic (or anoxic) reactor, as shown in Fig. 8, PAOs utilize PHA
and PHB to convert orthophosphates to polyphosphates and store them in their
structure. Through sludge removal, the phosphorus concentration in the wastewater
is decreased to the desired level.
Oxygen and nitrate are, respectively, electron acceptors in the aerobic and anoxic
zones, but in the anaerobic zone, PHA synthesis needs a source of reducing power
(Seviour et al. 2003). There are various suggestions about derivation of the required
electrons in anaerobic reactors. Comeau et al. suggested the tricarboxylic acid (TCA)
cycle which is shown in the Fig. 9 (Comeau et al. 1986). Bacteria use three main
procedures to maintain the proton motive force (pmf) (Comeau et al. 1986): (1) the
first method drives out the H+ from the cell when a carbon substrate and an electron
Fig. 7 Biological
phosphorus removal
microbiology – anaerobic
zone, Reproduced with
permission from (Seviour
et al. 2003)
Fig. 8 Biological phosphorus

removal microbiology –
aerobic zone, Reproduced
with permission from
(Seviour et al. 2003)
acceptor (oxygen in aerobic zone and nitrate in anoxic zone) are present. In this
process, nicotinamide adenine dinucleotide (NADH) plays the electron donor role
and is produced via glycolysis and/or TCA cycle. (2) In the absence of electron
acceptors, ATP breakdown at the ATP-ase site takes place to displace protons.
(3) The enzyme NADH-transhydrogenase breaks down NADH to NAD+ to transfer
protons.
Mino et al. suggested that Glycogen degrades anaerobically to generate electrons
for PHA synthesis (Mino et al. 1998). This process is illustrated schematically in the
Fig. 10.
Fig. 11 illustrates the PHB synthesis pathway. PHB is produced in a three steps
synthesis pathway. In the first step, two Acetyl-CoA coupled to form Acetoacetyl-CoA
Fig. 9 Bacterial strategies to maintain proton motive force, Reproduced with permission from
(Comeau et al. 1986)
Fig. 10 Biochemical model for the anaerobic uptake of organic substrates and their conversion to
PHA by PAOs, Reproduced with permission from (Mino et al. 1998)
Fig. 11 PHB metabolic pathway, Reproduced with permission from (Kessler and Witholt 2001)
by β-ketothiolase catalysis. Then, Acetoacetyl-CoA reduced to (R)-3-

hydroxybutyryl-CoA by NADPH-dependent acetoacetyl-CoA reductase catalysis.
Finally, (R)-3-hydroxybutyryl-CoA molecules polymerize to PHB. Dashed arrows
illustrate the negative regulatory of HSCoA and NADPH on β-Ketothiolase and
citrate synthase, respectively (Kessler and Witholt 2001).
Acinetobacter bacteria, Aeromonas, and Pseudomonas are kinds of bacteria
which can store polyphosphates and carbon in the form of PHB; hence, these
bacteria are responsible for biological phosphorous removal (Comeau et al. 1986).
Sidat et al. have prepared a table containing different organisms and their phospho-
rus uptake (Sidat et al. 1999).
Effects of Environmental Conditions on Phosphorus Removal

Mamais and Jenkins (1992) examined the effects of temperature and solid retention
time (SRT) on EBPR. Tests were performed as batch experiments at 10–37 C. The
optimum temperature for aerobic phosphorus removal was between 28 C and
33 C. SRT values were in the range of 2–4 days, and EBPR efficiency was
independent of SRT values until the SRT values were regulated above 2.9 days
(Mamais and Jenkins 1992). Smolder et al. (1994) investigated pH effects on
phosphorous release, which illustrated that P-release in the anaerobic zone is criti-
cally affected by the pH (varied between 5.5 and 8.5) resulting in a variation of
0.25–0.75 p-mol/C-mol (Smolders et al. 1994). Also, phosphorus release in the
anaerobic zone is increased as the pH is increased (Mulkerrins et al. 2004).
Dissolved oxygen (DO) in the anaerobic zone must be negligible (0.0–0.2 mg/l
oxygen), and it is highly recommended that DO in the aerobic condition be in the
range of 3.0–4.0 mg/l. DO values which are above of 4.0 mg/l are wasteful since it
cannot induce biological phosphorus removal (therefore the energy used to increase
the DO above 4.0 mg/l is wasted). The ratio of phosphorus to total organic carbon
(TOC) is another important parameter. When low P/TOC in the influent is utilized,
PAOs growth is suppressed, and obviously high P/TOC increases the growth of
PAOs over glycogen accumulating organisms (GAOs) (Mulkerrins et al. 2004).
Importance of Acetate in Biological Phosphorus Removal

Comeau et al., in a biological phosphorus removal plant, evaluated the concentration
of phosphorus, oxidized nitrogen, and PHB of three samples during 8 h of experi-
ment in three agitated but not aerated containers. Initially, three solutions of sodium
acetate (0, 30, and 60 mg/l acetate as HAc) were added to the containers. Subse-
quently, a solution of sodium nitrate (10 mg/l nitrate as N) was added after 4 h. They
illustrated the changes of these variables according to time. Regarding their obser-
vations, acetate presence and increase in its concentration causes enhancement in
PHB production, and polyphosphates highly convert to orthophosphates and also
increase reduction of nitrate to nitrite or gaseous nitrogen. While nitrate addition has
opposite effects since phosphate and PHB are uptaken by biomass, and also deni-
trification and biological phosphorus removal (bio-P) bacteria enter the competition
for available substrates (Comeau et al. 1987).
Biological Nitrogen Removal
Nitrogen is a nutritious element for humans, animals, and plants, which occupies
approximately 80% of the atmosphere. The main source of nitrogen in wastewater is
from human activities such as cooking, bathing, and waste disposal. Nitrogen exists
in the environment in the forms of organic nitrogen and inorganic nitrogen which
consists of ammonium (NH4+), nitrate (NO3), nitrite (NO2), nitrous oxide (N2O),
nitric oxide (NO), and gaseous nitrogen (N2). The various processes of the nitrogen
cycle are fixation, ammonification, nitrification, and denitrification which allow for
the circulation of nitrogen in the entire ecosystem. Figure 12 shows the nitrogen
cycle in nature.
Kjeldahl Nitrogen (KNT) is the sum of organic nitrogen and ammonium which
was developed by Johan Kjeldahl in 1883. Nitrogen mostly enters wastewater in the
form of organic nitrogen and ammonium. Ammonium is derived from breaking
down of urea. Total Nitrogen (TN) is the sum of KTN, nitrate, and nitrite.
Source of Nitrogen in Wastewater
Municipal, petrochemical, agricultural, food industry, paper making, leather making,

artillery making, and slaughterhouse wastewaters and leachate of solid wastes have
Fig. 12 The nitrogen cycle in nature, Reproduced with permission from (Stein and Klotz 2016)
various specific amounts of nitrogen. Fertilizers have great amounts of nitrogen in

their structures which can pollute run-offs or ground waters.
Importance of Nitrogen Removal
As it mentioned in section “The Importance of Nitrogen and Phosphorus Removal,”

nitrogen causes some irreparable problems in the water such as eutrophication which
increases water turbidity, decreases dissolved oxygen, and degrades water quality
leading to human health hazards, especially for the cardiovascular system.
Chemical Removal of Nitrogen: Advantages and Disadvantages
As explained in section “Types of Biological Nutrient Removal Systems,” there are

several chemical and physical methods for nitrogen removal. In the following, the
advantages and disadvantages of these methods are summarized.
The advantages of the ion exchange method are insensitivity to temperature,
ammonium removal up to required standards, operation even with substantial total
dissolved solids (TDS), not forming harmful compounds; on the other hand, this
method’s demerits are requiring reclamation, reduction of efficiency due to dissolved
solids, sensitivity to organic compounds and particles, and high cost of construction
and operation. Alternatively, the air stripping process removes ammonium and
phosphorus up to intended standards and is not susceptible to toxic materials, but
requires huge amounts of aeration and chemical compounds for pH regulation. Also,
this process is sensitive to low temperatures. Breakpoint chlorination’s advantages

are high removal of ammonium, demanding a small space, insensitivity to high
temperatures and toxic materials, and disinfection of the effluent. On the other hand,
considering chlorine consumption, this process is costly and produces
trihalomethanes.
Biological Nitrogen Removal Process
Biological nitrogen removal from wastewater follows two mechanisms: (1) biomass
synthesis and (2) nitrification–denitrification.
Nitrification–Denitrification
Nitrification
The main source of nitrogen in sewage is ammonium. Nitrification is a biological
process oxidizing ammonium to nitrite and then nitrite to nitrate. Bacteria responsi-
ble for the nitrification process are mostly autotrophs, while there are some hetero-
trophs as well. Autotroph bacteria utilize carbon dioxide as carbon source and gain
their required energy from inorganic compounds, while heterotrophs gain their
energy and carbon from organic compounds. The nitrification process consists of
two steps. Firstly, ammonia oxidizing bacteria (AOB) oxidize ammonium to nitrite.
These kinds of bacteria are nitroso organisms which include nitrosomonas,
nitrosospiras, and nitrosococcus. The following equation shows the nitrification
process.
2NH4 þ 3O2 ! 2NO þ

2 þ 2H2 O þ 4H þ New cells (2)
Secondly, nitrite oxidizing bacteria (NOB) oxidize nitrite to nitrate. These kinds
of bacteria are nitro-organism which include nitrobacter, nitrospira, nitrococcus, and
nitrospina. The following equation shows the process:
2NO
2 þ O2 ! 2NO3 þ New cells (3)
Koops and Pommerening-Röser (2001) investigated the distribution and eco-

physiology of ammonia-oxidizing and nitrite-oxidizing bacteria. Ecophysiological
parameters and preferred habitats of ammonia-oxidizing and nitrite-oxidizing bac-
teria are, respectively, illustrated in Figs. 13 and 14 (Koops and Pommerening-Röser
2001).
Effects of Environmental Conditions on Nitrification Process

Nitrification is sensitive to pH and the rate of nitrification declines when pH values
decrease, with nitrification practically ceasing under pH 6.0. The optimum pH is
between 7.5 and 9.0 (Mulkerrins et al. 2004). Long aeration times and SRT induce
complete nitrification. DO in the nitrification zone (aerobic condition) should be
64
The Modified Bardenpho Process
Fig. 13 Dendrogram based on 16S rDNA sequences of ammonia-oxidizing bacteria, Reproduced with permission from (Koops and Pommerening-Röser 2001)
1571
1572
Fig. 14 Dendrogram based on 16S rDNA sequences of nitrite-oxidizing bacteria, Reproduced with permission from (Koops and Pommerening-Röser 2001)
E. Banayan Esfahani et al.
between 2 and 4 mg/l. Also, since the growth rate of nitrifiers is lower than
heterotrophs, long SRT is mandatory for the nitrification process. Similar to phos-
phorus removal, the recommended mixed liquor suspended solid (MLSS) should be
between 1500 and 1700 mg/l (Mulkerrins et al. 2004). Increase in temperature
causes enhancement in the nitrification rate up to the optimum temperature of
30–35 C (Jeyanayagam 2005). Temperature affects microbial growth mechanism
and mass transfer of oxygen. Nitrifiers are highly sensitive to environmental inhib-
itors such as heavy metals and some organic compounds (Tomlinson et al. 1966).
Denitrification
Nitrification is followed by denitrification in order to remove nitrogen from waste-
water. In the denitrification process, nitrate is reduced to gaseous nitrogen (N2), and
consequently N2 is released to the atmosphere. Denitrification process requires
anoxic conditions. The following equation illustrates the overall denitrification
process in which various reductions take place: nitrate to nitrite, nitrite to nitric
oxide, nitric oxide to nitrous oxide, and nitrous oxide to gaseous nitrogen.
NO
3 ! NO2 ! NO ! N2 O ! N2 (4)
Bacteria responsible in the denitrification process are heterotrophs which include

thiobacillus, micrococcus, serratia, and pseudomonas reducing nitrate and/or nitrite
in the absence of dissolved oxygen. Pseudomonas are the most common denitrifiers
which can utilize various energy sources.
In the denitrification process, wastewater alkalinity increases and carbon dioxide
decreases. Carbon dioxide reduction causes pH increase which is the opposite of the
nitrification process; so, one of the most significant advantages of the denitrification
process is pH regulating which inhibits corrosion of treatment plant facilities like
piping and pumps.
Effects of Environmental Conditions on the Denitrification Process

Optimum pH for the denitrification process is between 7.0 and 8.0 (Mulkerrins et al.
2004). Increasing wastewater temperatures induces microbial activity and as a result
the rate of denitrification is enhanced. For instance, reduction in wastewater temper-
ature from 20 C to 10 C reduces the denitrification rate by up to 75%
(Jeyanayagam 2005). Due to the heterotrophic nature of denitrifiers, one of the
most effective parameters on denitrifiers’ performance is the ratio of BOD or COD
to TKN, with higher ratios of BOD to TKN causing higher denitrification
(Jeyanayagam 2005).
Types of Biological Processes
Different wastewater unit operations exist that utilize biological processes to remove
pollutants from wastewater such as trickling filters (TF), rotating biological
contactors (RBC), moving bed bioreactors (MBBR), activated sludge process
(ASP), and aerobic and anaerobic fluid beds. According to the growth condition of
microorganisms, these systems are divided into two general categories which are
suspended growth and attached growth. In suspended growth processes, microor-
ganisms are suspended in the wastewater during biological operation, and recycling
of deposited biomass is mandatory. In attached growth, microorganisms are attached
to a media such as polymeric, ceramic, or rocky bed to grow on their surface, and
microorganism recycling is not necessary. Microorganisms form a microbial layer on
the surface of the media and treat wastewater by this biofilm.
Set-up, control, and managing biofilm systems are easier. Since microorganisms
are attached to media, fluid flow cannot wash the biomass out of the wastewater
treatment plant, and microorganism recycling is not required. Also, the effluent of
the attached growth system has a better quality than suspended growth in terms of
microbial contamination. Biofilm processes have an operational benefit that excess
sludge production is lower in this process when compared to suspended growth
processes. But regarding to utilized media, costs of biofilm processes are usually
more than suspended growth systems.
Suspended Growth Processes
Microorganisms in suspended growth processes such as the activated sludge process

(ASP) are suspended in the unit in order to hydrolyze and consequently remove
pollution such as organic matter, nitrogen and phosphorous. Microorganisms are
mixed in the tank with aeration in aerobic zones, or with agitators in the anaerobic or
anoxic zones. As wastewater flows through the suspended growth tank, food (COD
or organic compounds) decreases due to microbial activity and cell mass is
increased. For instance, in the ASP, biomass oxidize organic material to grow and
form flocs of biofilms (Dabi 2015). The aeration not only provides oxygen as an
electron acceptor but also mixes the suspended microorganisms. Subsequently, the
mixture of treated wastewater and biomass flocs pass to the clarifier unit in which
microorganism and wastewater flow are separated. The sludge is either returned to
the aeration tank to increase the biomass concentration (MLSS) to the required level,
or discarded when the biomass concentration in the tank is adequate. Figure 15
illustrates an activated sludge schematic.
Attached Growth Processes
Biomass attach and grow on the surface of different media in attached growth
processes. These media have different shapes and are made of different materials,
all having high surface to volume ratios to support microorganism growth. Unlike
suspended growth processes, the substrate and oxygen must transfer from the
wastewater to the media and diffuse through the biofilm layers to be available for
all microorganisms. Subsequently, products of microbial activity follow diverse
routes from the biofilm to the wastewater (Jenkins and Sanders 2012).
Activated Sludge
Process
Clarifier
Influent Effluent
Aeration
Returned Activated Excess

Sludge Sludge
Fig. 15 Activated sludge process, Reproduced with permission from (Kayser 2005)
Kumar et al. (2009) investigated bacterial dynamics of living cells and dead cells
in a biofilm membrane bioreactor by confocal laser scanning microscopy (CLSM)
counts and considered 5 stages for microorganism growth and detachment during
biofilm developments (Kumar et al. 2009). These steps are, respectively, cell attach-
ment, pollutant limitation, biofilm stabilization and colonization, colonized biofilm,
biofilm erosion. Burkholderia Vietnamiensis G4 bacteria (BVG4) are utilized to
biodegrade the toluene as an impurity and also energy source in the wastewater. The
investigations proved that living and dead cells have a direct relation with the
efficiency of toluene removal (Kumar et al. 2009).
Worden and Donaldson (1987) developed governing equations for the biofilm
phase, wastewater phase and biomass growth in a well-mixed reactor for phenol
oxidation. In this research, the biofilm grew on coal particles (Worden and
Donaldson 1987). Horn et al. (2003) analyzed biofilm growth stages in homogenous
growth, quasi steady state, and washout experiments (Horn et al. 2003).
A trickling filter is a kind of attached growth processes in which wastewater is
sprinkled on the top of the filter media and flows downward through the media due
to gravitational force. The trickling filter provides an appropriate surface for
microorganisms’ growth, and wastewater flow provides oxygen and energy
sources for this purpose. Limitation in oxygen and energy source transfer, low
pace of biofilm growth, and clogging of the filters are some of trickling filters’
problems (Fig. 16).
Due to the above-mentioned problems associated with trickling filters, rotating
biological contactors (RBCs) which consist of many disks rotating on one axis to
provide the required surface for microorganism growth emerged in the 1960s and
1970s (Jenkins and Sanders 2012). In this system, due to the rotation of half-
submerged disks around a shaft, microorganisms obtain their necessary carbon
source from the wastewater and required oxygen from the air (Fig. 17).
Up-flow anaerobic fixed bed (UAFB) is another attached growth process in which
wastewater flows upward through the bed under anaerobic conditions. Zayen et al. (2016)
Fig. 16 A trickling filter, Reproduced with permission from (Filipe and Grady 1998)
Fig. 17 A rotating biological contactor, Reproduced with permission from (Filipe and Grady 1998)
used UAFB for landfill leachate treatment. They concluded that UAFB has a great
COD removal efficiency and biogas production (Zayen et al. 2016) (Fig. 18).
A moving bed biofilm reactor (MBBR) is another attached growth system in
which microorganisms grow on media as the wastewater smoothly moves through
them, since their density is near water density. Unlike the trickling filter in which
fixed media are utilized, in the MBBR system biomass grow on free-floating media
such as small plastic carriers. These media are moved around the aerobic tanks by
aeration and around the anoxic and anaerobic tanks by mixers (Fig. 19). This system
Fig. 18 An up-flow
anaerobic fixed bed,
Reproduced with permission
from (Zayen et al. 2016)
Fig. 19 A moving bed biofilm reactor. (a) Aerobic reactor, (b) anaerobic and anoxic reactor,
Reproduced with permission from (Rusten et al. 2006)
was first developed in Norway (Seviour et al. 2003), and the media utilized in them
were marketed as Kaldnes media which is shown in Fig. 20. MBBRs are very
flexible systems which can be utilized for various purposes such as organic com-
pound oxidation, nitrification, denitrification, and phosphorous removal. High
microbial activity, relatively small reactors, low energy consumption, and low sludge
production are some of important merits of moving bed biofilm reactors, while the
cost of media might be a hindrance, and set-up and control of these systems take
times and needs specific skills.
Fig. 20 Kaldnes media
Fig. 21 An integrated fixed-film activated sludge process, Reproduced with permission from
(Borner and Trubenbach 2017)
An integrated fixed-film activated sludge (IFAS) system is a combination

of suspended and attached growth systems. This system provides excess biomass
for an activated sludge process to enhance system capacity. This approach is mainly
used for aerobic zones and can be used for upgrading systems to increase biological
oxygen demand (BOD) removal and nitrification (Jenkins and Sanders 2012). Acti-
vated sludge is returned in this system to enhance biomass concentration in the tank,
and microorganisms’ carriers are either fixed or free-floating media. Figure 21
illustrates an integrated fixed-film activated sludge.
Performance of the Modified Bardenpho Process
The Modified Bardenpho Process is a biological approach combining

both nitrogen and phosphorus removal process configurations together. This
system consists of 5 distinct reactors in each of which special environmental
conditions are provided for biomass growth and removal of waste-

water impurities, especially nitrogen and phosphorus, with high effic-
iency. The Modified Bardenpho zones are, respectively: anaerobic reactor, first
anoxic reactor, first aerobic reactor, second anoxic reactor, and second aerobic
reactor.
As it was mentioned in previous sections, phosphorus biological removal is
highly dependent on PAOs’ function in absorbing energy and carbon sources
and hydrolyzing polyphosphates to organophosphates in the anaerobic zone and
using energy and carbon sources and up-taking polyphosphates in the aerobic
zone; so, biological phosphorus removal units should include anaerobic and
aerobic reactors. While for the biological nitrogen removal process, providing
appropriate conditions for nitrification and denitrification is a mandatory
requirement. As nitrification and denitrification processes, respectively, take
place in aerobic and anoxic zones, these two conditions are required, too.
Therefore, all three biological conditions – anaerobic, anoxic, and aerobic
conditions – are necessary in simultaneous removal of nitrogen and phospho-
rus, but what was the reason of this sequence in the Modified Bardenpho
process?
The Modified Ludzak-Ettinger (MLE) process is a biological process to
remove nitrogen with nitrification and denitrification processes. In this process,
an aerobic tank is placed after the anoxic zone since if the aerobic zone is the
first step, the oxygen concentration in sewage increases and disrupts the
denitrification process. Also, in order to complete the nitrification-denitrification
cycle, a recycle flow from aerobic zone to the anoxic zone is mandatory.
Considering the MLE, Barnard devised a 4-stage Bardenpho by adding an
anoxic and an aerobic reactor to the MLE process in order to enhance bio-
logical nitrogen removal so excess nitrate in the first aeration zone could be
reduced to gaseous nitrogen. Subsequently, Barnard realized the importance
of the presence of an anaerobic reactor in phosphorus removal; so, he
decided to put an anaerobic zone ahead of the 4-stage Bardenpho to increase the
efficacy.
Wastewater flow through the modified Bardenpho process can be provided by
gravitational force, while an important recycle flow from the first aerobic zone to first
anoxic zone should be considered which is usually provided by pumping. Figure 22
illustrates the modified Bardenpho process and wastewater flow through all reactors.
In the following, all 5 stages of the modified Bardenpho process are discussed in
detail.
Reactors in the Modified Bardenpho Process
Anaerobic Reactor
The first reactor in the modified Bardenpho process is an anaerobic
reactor (depleted of oxygen or oxidized nitrogen). In this reactor, mixers circulate
wastewater in a tank in order to deliver carbon and energy sources to all the
biomass.
1580
Pump
Recycle flow
Anaerobic Tank
Influent
1st Aerobic Tank
2nd Anoxic Tank

1st Anoxic Tank
2nd Aerobic Tank Clarifier
Effluent
Aeration
Aeration
Returned Excess
Fig. 22 The main flows in modified Bardenpho process

E. Banayan Esfahani et al.
• Function: Anaerobic zones provide appropriate conditions for phosphorus accu-

mulating organism (PAOs) growth and uptake of volatile fatty acids or other
carbon sources such as acetate to produce storable compounds such as PHA and
PHB. Also, polyphosphates are hydrolyzed to orthophosphates. The main pur-
pose of this step in the modified Bardenpho process is increasing phosphorus
removal efficiency. An important role of the anaerobic tank before the aerobic
tank is that oxygen concentration in the sewage is very low and it can increase
motive force of oxygen transfer in the aerobic tank.
• Environmental conditions: Phosphorus release in the anaerobic zone increases
as the pH increases. Also, ratio of the phosphorus concentration to the total
organic carbon concentration has a direct relation with PAOs growth and phos-
phorus removal.
• Contaminant concentration: Phosphate concentration in the anaerobic reactor is
significantly increased since it is released from polyphosphates. BOD and COD
amounts decrease since they are consumed as carbon sources. Nitrate, nitrite, and
DO concentrations are very low in the anaerobic zone. Ammonia concentration in
the anaerobic reactor is lower than the feed concentration but is higher than other
subsequent reactors.
First Anoxic Reactor

The second reactor in the modified Bardenpho process is the first anoxic reactor.
Effluent of the anaerobic reactor and recycle flow from the first aerobic reactor enter
this tank, and effluent of first the anoxic reactor flows to the first aerobic reactor. In
this reactor, dissolved oxygen should be low in order for the biomass to utilize
bonded oxygen in nitrate. If dissolved oxygen exists in the anoxic zone, biomass will
reduce oxygen as an electron acceptor and after depletion of oxygen, reduce nitrate;
hence, denitrification efficiency is declined. Mixers provide homogenous conditions
in all parts of the anoxic reactor.
• Function: The anoxic zone provides appropriate conditions for growth of deni-
trifiers. A group of heterotrophs such as pseudomonas reduce the nitrate and/or
nitrite in the absence of dissolved oxygen. The anoxic zone provides conditions
for the denitrification process to complete the nitrogen cycle and remove nitrogen
as a gas (N2). As a result, the recycle flow from the first aerobic zone to this
reactor is full of nitrate and denitrifiers reduce them in the denitrification process.
• Environmental conditions: Temperature has a direct relation with denitrifiers’
performance. It goes without saying that increasing the temperature increases
denitrifiers’ activity and denitrification. Optimum pH for the denitrification pro-
cess is a rather neutral pH between 7.0 and 8.0. Also, a high ratio of COD to TKN
stimulates denitrification.
• Contaminant concentration: COD and BOD amounts in this reactor are sub-
stantially reduced since denitrifiers utilize BOD and COD in the influent to reduce
nitrate to gaseous nitrogen. Nitrate and nitrite concentrations are very low in this
zone as well. Ammonia and phosphorus concentrations are lower than the
anaerobic reactor, but their concentration are still high.
First Aerobic Reactor

The third reactor in the modified Bardenpho process is the aeration or aerobic tank
which is aerated with air compressors. Aeration provides dissolved oxygen as an
electron acceptor in the biological nitrogen and phosphorus removal processes and
also provides mixing in the tank. This reactor, as the heart of the modified Bardenpho
process, plays the most important role in the performance of the unit. One reason is
that the first aerobic reactor provides appropriate conditions for PAOs to use carbon
sources such as PHA and PHB in order to absorb polyphosphates; so, phosphorus
concentration is significantly reduced in this section. Also, ammonia is oxidized to
nitrate through two reactions in which oxygen is as electron acceptor. In this way, the
aerobic tank provides conditions for the nitrification process. Finally, a proportion of
the effluent is sent to the first anoxic tank in order to reduce nitrate to gaseous
nitrogen.
• Function: The first aerobic reactor has two functions in the modified Bardenpho
process. Firstly, this reactor completes biological phosphorus removal since
orthophosphate in the sewage is absorbed and stored in biomass as poly-
phosphates. Secondly, this reactor helps the nitrification process in which nitroso
organisms such as nitrosomonas cause ammonia to oxidize into nitrite and nitro-
organisms such as nitrobacters cause nitrite oxidation to nitrate. In both these
reactions, oxygen performs as an electron acceptor and its existence is mandatory.
• Environmental conditions: Optimum pH for the nitrification process is near
neutral conditions between 7.5 and 9.0, and a reduction in pH reduces the
nitrification process. Dissolved oxygen concentration in the aerobic reactor
should be between 2 and 4 mg/l. Optimum temperature is between 30 C and
35 C.
• Contaminant concentration: BOD and COD amounts in the first aerobic zone
are significantly reduced since PAOs, nitroso, and nitrobacter organisms need
carbon sources for their growth and activity. Also, phosphorus concentration is
substantially reduced to the desired standards. Ammonia concentration is greatly
diminished since it is oxidized during the nitrification process, but nitrate con-
centration increases to its highest amount in the modified Bardenpho process.
Nitrite concentration is increased a little, too.
Second Anoxic Reactor

Actually, the main difference between the modified Bardenpho process and the A2/O
or 3-stage Phoredox system, which consist of anaerobic, anoxic, and aerobic reac-
tors, is the 4th and 5th steps of the modified Bardenpho process which are the second
anoxic and second aerobic reactors. The fourth reactor in the modified Bardenpho
process is the second anoxic reactor which provides another anoxic tank for
unreduced nitrate which has not been recycled to the first anoxic reactor and has
flown directly out from the first aerobic reactor; hence, it can improve biological
nitrogen removal in the modified Bardenpho process in comparison to A2/O or 3-stage
Phoredox reactors.
• Function: The second anoxic zone truly enhances biological nitrogen removal in
the modified Bardenpho process since unrecycled nitrate is reduced.
• Environmental condition: The required environmental conditions in the second
anoxic tank are similar to the first anoxic reactor.
• Contaminant concentration: BOD and COD amounts in the influent of the
second anoxic reactor are very low, but their amounts are reduced further in this
step. If anaerobic conditions are created in some parts of the anoxic reactor,
orthophosphate may release and phosphorus concentration may increase a little in
this section, while in the following second aerobic tank released phosphorus is
absorbed as polyphosphates and removed.
Second Aerobic Reactor

The final stage in the modified Bardenpho process is an aerobic reactor which aerates
wastewater in order to increase oxygen concentration and enhance wastewater
quality. Also, the presence of oxygen can decrease phosphorus concentration, if
any phosphorus is generated during the second anoxic tank or at the septic or clarifier
tanks.
• Function: As mentioned above, the second aerobic tank increases oxygen

concentration in the wastewater to improve wastewater quality as the final
stage and also inhibit phosphorus release in the next steps of the WWTP. In
biological phosphorus removal, it is mandatory to waste sludge in the aerobic
zone because sludge contains the maximum amount of the phosphorus
(Mulkerrins et al. 2004).
• Environmental conditions: The required environmental conditions in the sec-
ond aerobic tank are similar to the first aerobic reactor.
• Contaminant concentration: Similar to previous stages, microorganisms use up
BOD and COD as a carbon source for their growth. Also, the phosphorus amount
reaches its lowest value. Total nitrogen concentration in the influent and also the
effluent of the second aerobic reactor is very low, and in effect all contaminations’
concentrations have reached their desired levels.
In addition to the reactors discussed above, there are some other required
facilities such as at least two pumps for wastewater circulation from the first
aerobic reactor to the first anoxic reactor and from the precipitated sludge in the
clarifier to the anaerobic tank to return sludge. Also, the two aerobic tanks need
air compressors and diffusers, while the anaerobic and anoxic tanks require
mixers. Wastewater recycle flow from first the aerobic to the first anoxic tank
needs an adjustable reservoir tank since wastewater flow from the aerobic tank
is saturated with dissolved oxygen, and DO should be minimized before
entering the anoxic tank. Furthermore, similar to all wastewater treatment
units, the modified Bardenpho process needs appropriate piping, heaters or
coolers to adjust temperature and chemical compounds, and tanks for
adjusting pH.
Comparison of the Modified Bardenpho Process with Other BNR

Systems
A wide range of chemical and physical, environmental and operational parameters

such as hydraulic retention time, influent distribution, temperature, pH, recycling
ratio and so on determine the performance of biological nutrient removal (BNR)
systems; therefore, comparison of the modified Bardenpho process function with
other BNR systems requires an investigation in which nitrogen and phosphorus
removal efficiencies are compared in equal or analogous aforementioned parameters.
In what follows, biological nutrient removal efficiencies of different BNR systems
will be compared by mentioning some experiments’ results which compare two or
more processes and general comparison of advantages and limitations of BNR
processes.
As it stated before, BNR processes are divided into three categories. Some BNR
processes like modified Ludzack and Ettinger (MLE) process include anoxic and
aerobic tanks and remove only nitrogen. Austin and Nivala compared energy and
area requirement of MLE process with some wetland processes like aerated, tidal flow
and pulsed flow wetlands and concluded that MLE process has the highest energy
requirement and needs the lowest area in comparison to wetland processes (Austin and
Nivala 2009). On the other hand, the biological phosphorus removal processes are
highly dependent on the presence of anaerobic condition prior to the anoxic or aerobic
reactors. Lee et al. compared phosphorous removal between different BNR processes.
They concluded that both anaerobic/aerobic (A/O) and anaerobic/anoxic/aerobic
(A2/O) processes are dependent on influent COD/TP ratio, but in the same COD/TP
ratio (=44) A/O process has higher phosphorus removal efficiency than A2/O.
Therefore, A2/O process requires higher COD/TP ratio to remove phosphorus effi-
ciently. Also, in comparison between A/O and Phostrip processes in lower COD/TP
ratio (=25), Phostrip process phosphorus removal efficiency remains high while A/O
removal efficiency is dramatically decreased (Lee at al. 1997). The third category of
BNR processes remove nitrogen and phosphorus simultaneously such as modified
Bardenpho process which provide all biological conditions to remove nutrients. In a
comprehensive investigation, Ontiveros and Campanella compared various aspects of
conventional, modified University of Cape Town and modified Bardenpho processes.
In comparison with the conventional process, nitrogen removal efficiencies of mod-
ified University of Cape Town and modified Bardenpho process are respectively 60%
and 85%, while phosphorus removal efficiencies are respectively 51% and 24%. Also,
according to land use, climate change, eutrophication potential and some toxicity
aspects, modified Bardenpho process illustrated the most environmentally friendly
alternative (Ontiveros and Campanella 2013)
Jeyanayagam (2005) and Linden et al. (2001) provided general comparisons
between different BNR processes. According to these investigations, modified
Bardenpho process has an excellent performance in biological nitrogen removal
and lower efficiency in biological phosphorus removal. Also, large reactor volume
requirement can be mentioned as one of the most significant limitations of this
process (Jeyanayagam 2005; Linden et al. 2001).
Modified Bardenpho Process Design
The modified Bardenpho process as a biological system has various complications in

design since it has 5 distinct bioreactors, and every reactor has especial functions and
required conditions. For instance, even the two aerobic reactors or two anoxic
reactors have different applications and responsibilities in the modified Bardenpho
process, and as a result their specifications are different. Also, beside wastewater
flow, there is a significant recycle flow from the first aerobic reactor to the first anoxic
reactor which plays a prominent role in nitrogen removal. There are some imperative
parameters in designing modified Bardenpho process as discussed below.
Nutrient Removal Establishment
Start-up of every wastewater treatment unit, especially biological plants, takes time in
order to habituate microorganisms with environmental conditions such as the COD/N/P
ratio of the wastewater influent and the kinds of contaminations. Oldham and Stevens
(1984) studied commissioning a new wastewater treatment plant with the modified
Bardenpho process in Kelowna, British Colombia (Oldham and Stevens 1984). They
illustrated that the biological nitrogen removal process (nitrification and denitrification)
was established within 1 month of plant start-up, and nitrogen concentration in the
effluent was lower than 5 mg/l with an influent of 30 mg/l. Also, 2 months of operating
time was needed to steady out the phosphorus removal process, and phosphorus
concentration declined from 6 mg/l in the influent to less than 0.5 mg/l in the effluent
(Oldham and Stevens 1984). Due to the complexity of the modified Bardenpho process,
a small physical problem can decrease nutrient removal of the plant and cause irregular
results in some points. For instance, when air supply is out of service in first the aerobic
tank it can reduce both nitrogen and phosphorus removal efficiencies.
COD and Nutrient Ratio
Shortage of carbon, nitrogen, and phosphorus cause a wide range of problems, and
each tank optimally functions at a specific C:N:P ratio. For example, the effects of three
different influent C/N ratios on nutrient removal and the CO2, CH4, and N2O emission
rates were investigated. Higher C/N ratios (5:1 or 10:1) have higher removal efficien-
cies rather than lower C/N ratio (2.5:1). Also, moderate C/N ratio (5:1) illustrated better
greenhouse gas emission rates (Zhao et al. 2014). In another work, Puig et al.
investigated biological nutrient removal by sequence batch reactor (SBR) technology
and the effects of C/N/P ratio. According to the results, C/N/P ratioe of 100:12:1.8 in
the influent caused the successful biological nutrient removal (Puig et al. 2007).
Sewage of the modified Bardenpho plant of Oldham and Stevens (1984) had a
COD: NH3-N ratio of 9:1 (Oldham and Stevens 1984). Also, for efficient biological
phosphorus removal (phosphorus concentration in the effluent is lower than 1.0 mg/l),
the COD: P ratio should be higher than 40:1 (Mulkerrins et al. 2004).
Hydraulic Retention Time (HRT)
HRT is a paramount and influential parameter in designing wastewater treatment

plants since it designates the time that the wastewater remains in a reactor. HRT can
determine a reactors’ volume and consequently required constriction space and costs.
There is a common tendency to reduce reactors’ HRT, but hydraulic retention time
should be sufficient for the removal of the targeted impurities; so, one of the most
important design parameters that should be carefully evaluated is the HRT. Sakuma
(2005) studied hydraulic retention time effects of 7 different A2/O systems on phos-
phorus and nitrogen removal efficiency. The anaerobic, anoxic, and aerobic reactors’
HRTs are regulated, respectively, between 1.4 and 3.3 h, 1.7 and 6.1 h, 7.1 and 9.9 h.
The maximum phosphorus removal efficiency (91.4%) was obtained when anaerobic,
anoxic and aerobic reactors’ HRTs are, respectively, 1.4, 4.8, and 7.7 h, and the
maximum nitrogen removal efficiency (75.4%) was obtained when anaerobic, anoxic,
and aerobic reactors’ HRTs are, respectively, 1.5, 6.1, and 9.4 h.
HRT has critical influence on the BNR performance. Firstly, anaerobic reactor
retention times should be optimized since if HRT of the anaerobic tank is very low,
PAOs cannot produce storable carbon sources (PHA and PHB), and if the HRT of
anaerobic tanks is very high, PAOs substantially utilize COD of wastewater which
adversely affects the denitrification process. Also, long HRT is one of the main causes
of secondary P-release which occurs in the absence of VFA and adversely affects the
BPR process (Mulkerrins et al. 2004). Secondly, similar to the anaerobic reactor, the
anoxic reactor retention time should be optimized, since short HRT of the anoxic tank
causes improper denitrification and long HRT of anoxic tank harmfully affects phos-
phorus removal; denitrifying PAOs (DPAOs) are 40% less efficient in producing
energy and also 20–30% lower cell yield in comparison to PAOs (Patel et al. 2005).
Sludge Retention Time (SRT)
SRT is the average time which biomass stays in the system and is another important
parameter in designing biological nutrient removal systems. There are various
studies investigating SRT’s impact on BNR performances. Studies have illustrated
that SRT has two opposite influences: longer SRT causes better effluent quality,
while if the SRT is too long, it will cause high nitrification rates and a reduction in the
poly-P microbial fraction of the mixed culture. There are many investigations about
optimized SRT which have analyzed SRTs between 5 and 20 days, and have
suggested that in BPR systems the optimized SRT is approximately 10 days
(Mulkerrins et al. 2004).
Recycling Ratio (R)
The recycling flow is an effective wastewater flow from the first aerobic reactor to
the first anoxic reactor which completes the nitrification-denitrification process.
This is because the generated nitrate in the aerobic tank is reduced in the anoxic
tank to gaseous nitrogen and removed from the wastewater. The Recycling ratio
(R) should be optimized according to influent properties (Patel et al. 2005).
Nitrogen removal efficiency decreases with the increase of R at low COD/N ratios.
At medium COD/N ratios there is a peak. As the nitrogen removal efficiency
first increases and then decreases with the increase of R past the optimal point.
At high COD/N ratios an increase in R also increases the nitrogen removal
efficiency. Phosphorus removal efficiency generally increases with increase of R
(Patel et al. 2005).
Temperature, pH, and Bubble Size
Temperature and pH are two important parameters which should be measured

during wastewater treatment and set to the optimized values at which micro-
organisms have their highest performance. Optimum temperature and pH
for the anaerobic, anoxic, and aerobic reactors have been discussed in section
“Reactors in the Modified Bardenpho Process.” Also, the modified Bard-
enpho process consists of two aerobic reactors which require aeration. One
point regarding aeration needs particular attention: the bubble size. This is
because small bubbles have more efficient mass (oxygen) transfer to wastewater,
while large bubbles circulate wastewater or attached growth media better;
so, bubble size should not be very large or very small and should also be
optimized.
Modified Bardenpho Process Applications
The main application and purpose of the modified Bardenpho process is nutrient
removal. Meanwhile, due to the utilization of 5 biological stages, removing
other impurities such as chemical oxygen demand (COD), biological oxygen
demand (BOD), total suspended solids (TSS), heavy metals, and viruses can be
considered as added benefits of the modified Bardenpho process. In the following
sections, different applications of the modified Bardenpho process will be
touched upon.
COD, BOD, TSS, Nutrient, and Heavy Metal Removal
Emara et al. (2014) investigated the Fisha Selim wastewater treatment plant which
utilized rotating biological contactors (RBC) during 2013, but the effluent quality
was not pleasing. Average removal efficiencies of chemical oxygen demand (COD),
biochemical oxygen demand (BOD), total suspended solid (TSS), total nitrogen
(TN), and total phosphorus (TP) in this system were 82%, 86%, 63%, 54%, and
50%, respectively. In order to improve the effluent quality, a 4-stage Bardenpho and
a modified Bardenpho processes were designed. In this study, biological processes
were suspended growth such as the activated sludge process. COD, BOD, TSS, TN,
and TP removal efficiencies in the 4-stage Bardenpho process increased to 97%,
98%, 97%, 97%, and 50%, respectively, while these efficiencies in the modified
Bardenpho process dramatically increased to 99%, 99%, 99%, 99%, and 90%
(Emara et al. 2014). The modified Bardenpho process efficiency is on all accounts
higher, particularly for phosphorus removal.
Emara et al. (2014) also investigated nickel and iron contents in the wastewater
influent and effluent from various systems. They observed that the removal effi-
ciency of heavy metals from the Fisha Selim wastewater ranged between 10% and
30% in the RBC system (after 12 h), while the 4-stage Bardenpho and 5-stage
Bardenpho, respectively, removed these heavy metals by 70 and 90–100% after 14 h
(Emara et al. 2014).
Viruses Removal in Modified Bardenpho Process
The initial focus and purpose of the modified Bardenpho process is biological
nutrient removal, although a limited number of studies have pertained to virus
removal as a valuable side effect of this process.
A particular study compared virus removal via the modified Bardenpho process
as a secondary wastewater treatment approach to other conventional aeration basin
and trickling filter processes (Schmitz 2016). According to this study, the five-stage
Bardenpho process is more effective at reducing viruses in wastewater than other
conventional processes.
Before 2014, two conventional biological processes, the trickling filter, and
activated sludge aeration basin were utilized for secondary wastewater treatment in
Tucson, Arizona. In recent years, however, Tucson WWTPs have started to utilize
the modified Bardenpho process. In this way, a great opportunity for comparing
pathogen removal efficiency of the modified Bardenpho process with other conven-
tional biological processes came about (Schmitz 2016).
In the mentioned study, the removal of 11 different virus types (pepper mild
motlle virus, aichi virus, genogroup I, II, and IV noroviruses, enterovirus, sapovirus,
group-A rotavirus, denovirus, and JC and BK polyomaviruses) was analyzed in a
12-month period in southern Arizona. The results indicated that the modified
Bardenpho process had a higher efficiency in pathogenic virus removal than con-
ventional biological processes. In addition, the pepper mild mottle virus seemed to
be a useful process indicator in the investigation of virus removal during wastewater
treatment (Schmitz 2016).
According to this study, the five-stage Bardenpho process removes viruses by
adsorption onto the biomass flocs in various anaerobic, anoxic, and aerobic zones.
Actually, the modified Bardenpho provides more opportunity for virus adsorption to
suspended particles; so, viruses are not killed, but rather concentrated in the solid
phase and transformed to the sludge waste.
Results illustrated that average virus removal efficiency in the modified

Bardenpho process with sedimentation as preliminary treatment was 71.2% com-
pared to 44.9% and 47.9% for other conventional setups. Combing the modified
Bardenpho with a DAF system did not improve virus removal efficiency (Schmitz
2016).
Estimation of Greenhous Gas Emissions of Modified Bardenpho

Process
Recently, global warming has become one of the top concerns of all societies, and
greenhouse gas emissions are hypothesized to play a prominent role in this phenom-
enon. Wastewater treatment plants are a sources of greenhouse gas emissions since
during wastewater treatment, some greenhouse gases such as carbon dioxide (CO2),
methane (CH4), and nitrous oxide (N2O) are produced. Sources of greenhouse gases
are on-site and off-site in WWTPs. CO2, CH4, and N2O are by-products of biological
activities, while greenhouse gases can be generated from off-site sources such as
electrical and chemical operations that support the WWTPs (Kyung et al. 2015).
Kyung et al. (2015) developed a model to assess greenhouse gas emissions from
WWTPs. In this model, greenhouse gas emissions from a treatment plant consisting
of a clarifier, a modified Bardenpho process, second clarifier, filter bed, and an ultra-
violet disinfection system were determined. The aim of this WWTP was to remove
carbon, nitrogen, and phosphorus from 5500 m3/day wastewater with 200 mg/l
BOD. Each greenhouse gas emission is evaluated in every step of the modified
Bardenpho process, and on-site greenhouse gas emissions occur only in the primary
clarifier, modified Bardenpho process, and secondary clarifier but does to indirect
emissions (chemical and electricity production, building materials, transport, etc.) all
parts of the WWTP release off-site greenhouse gases. Table 2 illustrates greenhouse
gas emissions from primary on-site resources. Based on this table, the first aerobic
Table 2 On-site greenhouse emissions in a WWTP consisting of a clarifier, a modified Bardenpho

process, second clarifier, filter bed and an ultra-violet disinfection system, Reproduced with
permission from (Kyung et al. 2015)
CO2 emission CH4 emission N2O emission Total
Unit process (kgCO2/day) (kgCO2/day) (kgCO2/day) (kgCO2/day)
Primary 7.7 0.7 287 27 71.2 7.9 366 36
clarifier
Anaerobic 1.3 0.1 497 35 11.4 0.8 510 36
1st Anoxic 1.8 0.2 0.4 0.1 14.6 0.9 16.8 1.2
1st Aerobic 3673 265 776 58 2646 247 7095 570
2nd Anoxic 2.1 0.3 0.1 0.0 12.9 2.8 15.1 3.1
2nd Aerobic 2.3 0.3 0.6 0.1 6.5 0.7 9.4 1.1
Secondary 13.2 2.0 1.1 0.2 238 29 252 31
clarifier
Total 3701 269 1562 120 3001 289 8264 678
reactor is the main source of greenhouse gases, especially CO2 since in this step,
nitrification, BOD oxidation, and microorganism respiration are occurring. The
anaerobic reactor generates CH4 more than other gases, while anoxic reactors
produce higher amounts of N2O (Kyung et al. 2015).
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Diagnostic and Treatment by Different
Techniques of Leachates from Municipal 65
Solid Waste in Morocco Using Experimental
Design Methodology
Meriem Abouri, Salah Souabi, and M. Abdellah Bahlaoui
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1595
The Study Areas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1598
Sampling and Recovery of Leachates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1601
Chemical Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1602
Equipment and Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1606
Ventilation Device . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1607
Anaerobic Treatment Device Combined with Aerobic Treatment . . . . . . . . . . . . . . . . . . . . . . . . . 1607
Measurement of Global Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1608
Experimental Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1609
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1610
Characterization of Raw Leachate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1610
Characterization of Settled Leachate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1612
Application of Composite Plans for the Treatment of Leachate of MSW . . . . . . . . . . . . . . . . . 1614
Biological Treatment of Leachate from MSW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1623
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1627
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1629
Abstract
The management and treatment of leachate issues in Morocco are of technolog-
ical and environmental orders. Indeed, the pressure on the environment as on the
quality of life of the populations and health conditions are becoming more and
M. Abouri (*) · S. Souabi

Laboratory of Process Engineering and Environment, Faculty of Sciences and Techniques,
Mohammedia, University – Hassan II, Mohammedia, Morocco
e-mail: meriemabouri@hotmail.com
M. A. Bahlaoui
Laboratory of Materials, Catalysis and Development of Natural Resources, Faculty of Sciences and
Techniques, Mohammedia, University – Hassan II, Mohammedia, Morocco

https://doi.org/10.1007/978-3-319-73645-7_88
1594 M. Abouri et al.
more alarming, which directs researchers to find adequate solutions to the leach-
ate treatment with less expensive technology investment and exploitation.
The present work shows the results of leachate treatment coming from two
site: leachates from Municipal Solid Waste of the city Mohammedia and leachates
from the landfill of the city Kenitra by the coagulation flocculation process, using
several coagulants (FeCl3 a rejection of the steel industry rich in FeCl3 (SIWW),
Al(Cl)n) and flocculants (Himoloc DR3000 and cactus), by biological processes
(aerobic and anaerobic) and by physicochemical and biological techniques.
This study aims to implement a simple technique and less expensive invest-
ment and operation for the reduction of pollution of leachate based on the
Response Surface Methodology (RSM). The latter can significantly reduce the
time and cost. Tests are carried out in the laboratory to assess the optimal
conditions for effectively reducing pollution of leachate.
To achieve this goal, the mastery of pollution is needed to quantify the
different types of pollutants. Indeed, leachate discharges are rich in organic
matter, NH4+, detergents, phenols, etc. The results showed that the pH without
adding reagents has considerable influence on the reduction of pollution in terms
of COD, BOD5, NH4+, detergents, phenols, color, organic matter measured at
254 nm. The comparative study of treatment of leachate from MSW of the city of
Mohammedia and that of the discharge Ouled Berjal Kenitra by coagulation
flocculation process has shown that the effectiveness of the latter is based on
the quality of leachate selected for the study (stabilized leachate, slightly stabi-
lized, young, etc.). The optimal concentrations evaluated over time will vary with
the quality of leachate from Mohammedia and from landfill of the city of Kenitra.
The comparative study of different coagulants showed that removal of pollution
depends on coagulants, flocculants, pH, and function of the physicochemical
characteristics of leachate. Sludge formation is high at basic pH (700 ml/L),
whereas its production during coagulation flocculation is a function of nature of
coagulants and flocculants added. The optimization of the Response Surface
Methodology of coagulation flocculation process in the treatment of leachate
from municipal solid waste of city of Mohammedia by studying the combination
of coagulants and flocculants has allowed us the valuation of a biofloculant such
as cactus and a wastewater of steel industry rich in FeCl3.
The second technique concerns the treatment of leachate from Municipal Solid
Waste by aerobic and anaerobic biological pathway, on the one hand by studying
the evolution of indicators of pollution parameters such as COD, phenol, deter-
gent, and the ammonia in the absence and presence of ventilation, on the other
hand, the combination of anaerobic and aerobic treatment.
The technique using the continuous and discontinuous aeration significantly
reduced pollution leachate from the city of Mohammedia. Removal ranging
from 90% to 60% of surfactant was obtained during aeration of leachate from
MSW, while the phenol removal efficiency varies around 63%. Good reduction of
COD and BOD5 during aeration was obtained during the study cycle. In addition,
the treatment of leachate with a high organic load by the combined biological
process – anaerobic for 43 days followed by intensive aeration at 3.5 L of air per
65 Diagnostic and Treatment by Different Techniques of Leachates from. . . 1595
minute per 10 l of leachate over a period of 30 days – has allowed elimination of

75%, 66%, and 60% of the COD, BOD5, and turbidity, respectively, after 73 days.
Keywords
Leachate · Solid waste · Coagulation-flocculation · Biological treatment ·
Response surface methodology · Experimental design
Introduction
In Morocco, solid waste production is steadily increasing as a result of population

growth and the intensification of economic activity (Ez Zoubi et al. 2010).
According to these authors, this production is estimated at 4.5 million tons per
year of household waste and 800,000 tons per year of industrial waste. The rate of
waste production varies from one region to another and can vary from 0.6 to
0.7 kg/inhabitant/day (El Maguiri et al. 2014; Souabi et al. 2011; Tazi 2001). The
treatment of household waste, in particular, remains very little developed outside the
landfill, almost universalized by Moroccan municipalities. This method can no
longer survive in view of the significant damage it causes to the environment
(pollution of groundwater and surface water, soil pollution, impact on human health,
greenhouse gas emissions) (Idlahcen et al. 2014; Magda and Gaber 2015).
In the interior of the wild dumps, the dumped wastes are only rarely totally inert
and many physicochemical and biological reactions intervene between the waste and
the environment in which it is located (rock, soil, groundwater, seepage water), but
also within waste of various origins. The evolution of waste in landfills and their
interactions with the external environment lead to the dispersion of pollutant flows,
mainly through the emergence of leachate resulting from the dissolution of physi-
cochemical and biological elements pollutants in water percolation. This water is
loaded with organic and mineral substances and gives rise to leachates (Magda and
Gaber 2015). The infiltration of these pollutants into the water table or their flow to
the creek can lead to an insidious degradation of groundwater and surface water
(Idlahcen et al. 2014). In fact, surface water pollution by leachates may occur by
overflow and flow of liquids in the river system, either abruptly or gradually, whereas
groundwater pollution is the result of infiltration and the spread of leachate in
permeable or cracked subsoil (Souabi et al. 2010). The dissolution and chemical
precipitation mechanisms that occur during infiltration are closely related to the
physicochemical, biological, and hydrodynamic conditions of the aquifer system
compartments traversed by the leachate (soil, unsaturated zone, and saturated zone
of the aquifer), the latter regulating the attenuation, the transfer delay, the level of
propagation, and the definitive retention of the polluting product (Baun et al. 2004).
The risk of groundwater pollution from landfill leachate has been the subject of
several studies. Thus, since 1960, some authors (Magda and Gaber 2015; Renou
et al. 2008) have shown in their work that the pollution of the aquifer by the
discharge is almost undetectable; others (Ragle et al. 1995) have shown the presence
of a real hazard on many landfills studied in Wales and Canada.
At the level in Morocco, several studies are made on the characterization and
treatment of landfill leachates and household waste:
Chofqi et al. (2004) have shown that the uncontrolled landfill of El Jadida
generates stabilized leachates with a high nonweakly or poorly biodegradable,
undrained, pollutant leachate, which seeps through the subsoil and contaminates
the shallow circulating water table at the bottom of the quarries. Another study that
was done by the Ministry of Land Use Planning, Water and Environment (MATEE)
and the GTZ Management and Protection of the Environment Program (PGPE) in
2006 on the Tangier landfill shows that these leachates are generally loaded with
highly colored organic matter and increased levels of heavy metals (Chouaouta
2002). They are charged bacteriologically and especially chemically with substances
both mineral and organic. They can mix with both surface and groundwater and thus
constitute a pollutant element both in terms of quantity and quality (ecotoxicological
elements). El Kharmouz et al. (2013) studied the impact of leachates from the former
Oujda city dump on groundwater and surface water. They have found that these
leachates reveal high levels of biodegradable organic matter (BOD5 equal to
13,520 mg/l) and mineral matter (EC equal to 170 ms/cm) and that the analysis of
ground and surface water has levels in NO3- (50 mg/l), chloride (400 mg/l), and iron,
Zn, and Ni contents which far exceed the French standard values set for groundwater.
Souabi et al. (2010) did a study on the characterization of leachate from the city
dump of Mohammedia and Fez. The results of this study have highlighted the
pollution generated by leachates that affects surface water and groundwater. The
analysis of heavy metals in leachates has shown, according to the authors, a high
concentration of chromium (5 mg/l) in the case of the Mohammedia discharge and
9 mg/l of that of Fes, while the Pb reaches a maximum concentration of 2.1 mg/l for
the Fez landfill and 0.7 mg/l for the Mohammedia landfill.
Following the impact of leachate on the environment through percolation into the
groundwater and surface water pollution found in these previous studies, further
work is being done to address this leachate treatment problem to minimize impact
on the environment and human health. Benradi et al. (2013) studied the treatment of
leachate at the Intercommunal Waste Center of Oum Azza (Rabat-Morocco) by
reverse osmosis and the treatment of concentrate by the combination of coagulation
flocculation using chloride ferric FeCl3 as chemical coagulant followed by decanta-
tion. These authors found that this treatment made it possible to obtain a clarified
supernatant liquid with a decantation yield of up to 96%. Jirou et al. (2014) used
another method of treating leachates from fresh household waste received at the
Agadir city dump, using aeration to reduce the pollutant load of leachate. This
technique of air injection has given variable results depending on the importance
of the pollutant load and the chemical nature of the organic constituents. The
purification yields are quite high with 99.3% reductions in COD, 99.1% of BOD5,
94.4% of total nitrogen, and 82.9% of suspended solids. Zalaghi et al. (2014) studied
the characterization and treatment of leachate from the uncontrolled landfill in the
city of Taza. They evaluated the technical efficacy and socio-economic performance
of infiltration-percolation treatment on fixed natural supports appropriate to the
local context. This technique results in a reduction of the suspended matter (MES),
respectively, of the order of 90%, 93%, and 96%, a reduction of the chemical oxygen
demand (COD) of the order of 91%, 89%, and 83%, respectively, and a reduction,
respectively, of the order of 94%, 90%, and 91% in terms of the biological oxygen
demand (BOD5) at the outlet of the ash filter, clay, and that of the mixture of the two.
Benyoucef et al. (2015) have used another method of treating household waste
leachate from the city of Kasbah Tadla, that is, the technique UASB (Upflow
Anaerobic Sludge Blanket). The authors have shown that these leachates have
a high concentration of organic matter in COD of 12,240 mg O2/l and a high
acidity (pH = 5.16). According to the same authors, leachate treatment using the
UASB technique showed a 93% reduction in COD and a shift from pH to neutrality
(pH = 6.9). In addition, Bouaouine et al. (2015) studied the treatment of leachate
from the controlled public landfill of the city of Fez by the method of electro-
coagulation with the aluminum blades. The efficiency of the process is evaluated
in terms of metal pollution, turbidity, sludge production, absorbance, and color
removal. The results showed a significant elimination of metallic elements, in
particular As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn elements. The results also
showed that the elimination of Cr, Zn, Ni, and Fe varies, respectively, by 79%,
86%, 89%, and 90%.
Our present study targeted the leachate treatment produced by the cities
Mohammedia and Kenitra. The inhabitants of Mohammedia city produce an average
of 23,156 tons per year of waste, or 0.8 kg/inhabitant per day. The introduction of
selective collection will enable the recovery of 7687 tons/year of glass,
5109 tons/year of plastic, 8670 tons/year of cardboard, and paper, and 1690 tons/
year of metals (El Maguiri et al. 2014). This household waste mixed with industrial
waste is collected and transported to the public dump of the city Mohammedia.
Before their evacuation, this waste is compacted in order to minimize transport costs.
Leachate from compaction contains bacteriological, organic, and mineral pollutants.
The purpose of our study is to characterize the physicochemical quality of
leachates resulting from the compaction of municipal solid waste of Mohammedia
city and the leachates produced by the Kenitra city landfill, physicochemical and
biological treatment of effluent as well as improving the efficiency of pollution
removal efficiency through modeling and optimization using the Surface Response
Methodology (SRM) of the Coagulation Flocculation (CF) process.
The works carried out comprise three distinct parts. The first part presented in this
chapter deals with the materials and methods used for the treatment of leachates,
description of the study areas (Mohammedia city and Kenitra city discharge), the
sampling method and presentation of the different methods of analysis used, and
treatment techniques such as coagulation flocculation, aerobic, and anaerobic treat-
ment. In the second part, we touched on the practical side: results and discussion,
which spread over five subchapters:
The first subchapter deals with the characterization and treatment of the leachates
of the DSM of the city of Mohammedia and that of the Kenitra city discharge by
the flocculation coagulation process by studying the effect of pH and the effect of
the coagulants used (FeCl3 40%, polyaluminum chloride and SIWW) in terms of
concentration and composition.
The second subchapter examines the evolution of the concentration of phenol and
detergent in the leachate of the DSM of Mohammedia city in the absence and in the
presence of aeration as well as the biological treatment of this leachate by continuous
and discontinuous aeration.
The third subchapter focuses on anaerobic treatment combined with the aerobic
treatment of leachate from DSM Mohammedia city for the elimination of turbidity,
color, phenolic compounds, COD, BOD5, and nitrogen.
The fourth subchapter aims at the optimization by the Surface Response Meth-
odology of the Coagulation Flocculation Process in the treatment of the leachate of
DSM in the city of Mohammedia by studying the combination of coagulants (FeCl3
40%, SIWW, Al (Cl) n) and flocculants (Himoloc DR3000 and the cactus) in
the treatment of this leachate as well as the valorization of a biofloculant which is
the cactus and a FeCl3-rich rejection which is the SIWW.
The Study Areas
Mohammedia City
Mohammedia, formerly known as Fedala, is located on the coast of the Atlantic
Ocean, between two of the most important cities of Morocco: the economic city of
Casablanca (25 km to the east) and the administrative city of Rabat (65 km to
the west), of which it is connected by the coastal road 111 and the secondary road
107 in addition to the Casablanca-Rabat highway and a double-track rail link.
The city covers 34.03 km2 and is home to a population of 188,619 according to
the 2014 census.
The urban territory is divided into limited geographical areas, traditionally called
sectors. A containerization plan indicating the location, number, and capacity of the
installed bins is assigned to each area. The collection of these bins is done by a truck
benne equipped with a container lifter and a tank for the recovery of leachate
resulting from compaction of waste. This compaction is done at a transit station
before being sent to the landfill for the purpose of reducing the cost of transport.
Leachate composition is a function of the amount and composition of household
waste generated by the seasons and the type of habitat. (El Maguiri et al. 2014).
Table 1 shows that the majority of the household waste components of
Mohammedia city are organic materials varying around 44.36%.
The objective of this study is to treat leachate resulting from compaction of
this household waste. These very young leachates are rich in biodegradable
organic matter.
Kenitra City
The city of Kenitra is located 45 km north of Rabat, the capital. With an area of
76 km2, it is the fourth largest industrial city in the country and the capital of Gharb.
Table 1 Household Component Average (%)

waste components of
Organic mater 44.36
the city Mohammedia
(El Maguiri et al. 2014) Glass 9.78
Plastic bags 8.17
Hygienic textile 7.45
Plastic 6.50
Paper 5.87
Cardboard 5.16
Textile 3.05
Wood 2.48
Minority waste 2.23
Metals 2.15
Food packaging 1.90
Green waste 0.90
It is considered one of the largest Moroccan cities and one of the largest in the
north west of the Kingdom. Indeed, the city is on the south shore of the Oued
Sebou 12 km from the mouth on the Atlantic Ocean at Mehdya beach. It is located
in a crossroads of trade routes, connecting the cities of northern and eastern
Morocco.
The population is about 1,061,435, the climate is subhumid to semi-arid
influenced by the ocean, and the average rainfall is about 600 mm.
The city of Kenitra is characterized by two major phenomena:
• Unprecedented population growth

• Rapid expansion of the city
This translates into pressure on collective social amenities and hyperproduction

of solid waste. Annual production of household and similar waste is around
108,000 tons in 2004 and 120,000 tones in 2011.
To cope with the continuous increase in the volume of waste produced by its
population, the Urban Commune has entrusted the collection and cleaning service to
two professional operators: the company SEGEDEMA which operates in the
Mamora zone and the company TECMED which ensures the service in the Saknia
area (cost of collection and cleaning is in the order of 40 million DH and the cost of
landfilling at the landfill is 14 million DH) (Bolt et al. 2005). Table 2 illustrates the
physical composition of household waste at the Kenitra landfill.
Ouled Berjal Dumps

It is located northwest of the city of Kenitra on the secondary road from Kenitra to
Sidi Allal Tazi, on the left bank of the Oued Sebou estuary. It covers an area of 20 ha
and receives, on average, 329 tons per day and 120,000 tons per year of waste. Waste
management in the landfill is handled by SOS. Fig. 1 shows the Ouled Berjal dump
located in Kenitra.
Table 2 Physical Components Average (%)

composition of municipal
Organic waste 70
solid waste at the Kenitra
landfill (Aouane et al. Plastic 12
2010) Paperboard metals 10
Glass 2
Metals 4
Various (wood, etc.) 2
Fig. 1 The Ouled Berjal dump located in Kenitra city
The technical installations of this landfill consist of:
• Closing
• Administrative room for staff
• Landfill area consisting of a 4 hectare bin that is subdivided into 4 cells
• Three large ponds for leachate collection and one reserve pond:
– The first has a capacity of 21,945 m3 (105 55 3.8) and has built since the
year 2010.
– The second basin has a capacity of 7,363 m3 (39 59 3.2) and has been
built since 2012.
– The third basin has a capacity of 19,220 m3 (88 78 2.8) and has been built
since 2013.
– The fourth reserve basin has a capacity of 19,200 m3 (100 60 3.2) and has
been built since 2014.
• Conducting leachates and rainwater
Constraints:
• Location of the landfill in a vulnerable site

• Untreated leachate
• Ecological recuperators (scavengers) working in the informal sector
• Risk of saturation of the discharge
Sampling and Recovery of Leachates
The Dump Trucks

The leachates of the city Mohammedia were sampled from the dump trucks. These
trucks were chosen randomly, each truck has a capacity of about 3 tons.
The dumpsters are trucks adapted to the recovery of garbage. They are equipped
with an automatic recovery system adapted to the tank, equipped with a compacting
mechanism. They consist of a cab chassis to which the bodywork is attached, an
ejector plate in the body, a hydraulic system and a control mechanism. All functions
and the distribution of the load of the clamshell bucket are properly designed with
respect to the technical specifications of the chassis of the truck on which the bucket
is mounted. Fig. 2 shows an example of a dump truck.
In Situ Sampling: Case of the Kenitra City Landfill

Two types of leachate removal from the Ouled Berjal landfill were carried out:
• Sampling at 5 collectors in series (R1, R2, R3, R4, and R5 leachate) one time
• Sampling at 3 storage basins (B1, B2, and B3) in three times
Fig. 2 Dump truck

Leachate sampling is done in situ using a container in for each basin and from
each collector as shown in (Fig. 3).
Chemical Products
Ferric Chloride FeCl3 40%

Table 3 illustrates the physicochemical characterizations of the coagulant
FeCl3 40%:
Fig. 3 In situ sampling using a container
Table 3 Characterization of the coagulant FeCl3 40%

Determination Unit Data
Chemical formula – FeCl3
Appearance – Dark brown
Ferric chloride (FeCl3) % mass percentage 39.0–41.0
Iron (III) % mass percentage 13.4–14.2
Iron (II) % mass percentage of iron content (III) <2.5
Manganese <0.4
Insoluble matter <0.2
Density at 20 C kg/dm3 1400–1440
pH à 20 C – <1

Melting/freezing point C 12

Boiling point C 106
SIWW Steel Industry Wastewater Rich in FeCl3

The SIWW is a rejection of the steel industry Maghreb Steel and is rich in FeCl3
(29.5%). Anouzla (2014) used this coagulant in the treatment of liquid discharges
loaded with dyes; he detailed the origin of this rejection as follows:
Maghreb Steel
Maghreb Steel (Moroccan company) is an industrial company specializing in
the manufacture and marketing of cold-rolled, galvanized, and coated steel
sheet, intended for the realization of products for building, road equipment, metal
furniture, electrical equipment, and appliances.
The raw material used is in the form of hot-rolled coils. These are first etched
(operation of chemical cleaning of the steel by removal of superficial oxides with
the aid of hydrochloric acid), then laminated (reduction operation of the thick-
ness), galvanized (treatment which consists to heat-coat the surface of the cold-
rolled coil with a thin layer of zinc to protect the steel against corrosion), and
prepainted (deposition of liquid organic material suitable for nonaggressive
atmospheres in order to increase the resistance to corrosion and add an aesthetic
effect).
Origin of SIWW
The final step in the sheet-making process is the chemical treatment, consisting of
three trays intercalated by drive and traction rollers, fed with hydrochloric acid
mixed with filtered water, in order to obtain the desired dilution order at each tank
and heated by heat exchangers, in acid tanks with pumps ensuring the circulation in
content and the regeneration of the stripper.
The strip passes through three closed acid trays in which a chemical reaction
occurs between the stripper and the oxide to form ferric chlorides (FeCl3).
The source of rejection SIWW is the elimination of oxide layers by chemical
etching with hydrochloric acid following the reactions below:
Ferric oxide : Fe2 O þ 6HCL ! 2 FeCl3 þ 3H2 O
Magnetic oxide : Fe3 O4 þ 8HCl ! 2 FeCl3 þ FeCl2 þ 4H2 O
Ferrous oxide : Fe O þ 2HCl ! FeCl2 þ H2 O
Features of SIWW
The characteristics of SIWW are given in Table 4. This rejection has been valued as a
coagulant for the treatment of leachates since it is rich in FeCl3.
Polyaluminum Chloride Aln Cl 17%

The characteristics of Polyaluminum Chloride as a coagulant are shown in Table 5.
Table 4 Characterization Parameter Value

of the coagulant SIWW
pH <1
Conductivity (μs/cm) 20
Turbidity (NTU) 96.8
Fe3+ (g/l) 101.3
FeCl3 (g/l) 295
Table 5 Characteristics Appearance Yellowish liquid

of Polyaluminum
Aluminum (Al) 9.0 0.2%
Chloride
Al2O3 17.1 0.4%
Iron (Fe) <0.01%
Density (25 C) 1.37 0.03
pH 0.9 0.3
Basicity 42 2%
Active matter 3.33 moles/kg
Viscosity (25 C) 30 5 cP
Freezing point 20 C/4 f
Boiling point 110
Fig. 4 The prickly pear (Opuntia ficus-indica)
Cactus Juice
Fig. 4 shows the prickly pear (Opuntia ficus-indica) used in this study to extract the
juice used in the treatment of leachate.
Preparation of Cactus Juice

The prickly pear plant leaves (Fig. 4) used in the leachate treatment was milled after
washing with water several times. The aqueous plant extract is collected by sieving
on a 500 micron diameter filter (Fig. 5).
The cactus juice obtained is relatively stable. It can be kept flocculent capacity
outside any conservation system for several days. This product is a viscous liquid
of green color, pH = 6.5, miscible with water, with a specific gravity of 1.008 kg/l,
and contains about 96% of water. His analysis by UV spectroscopy gave the
spectrum in Fig. 6.
Himoloc DR3000 Flocculent

Himoloc DR3000 flocculent is a cationic polyacrylamide of medium molecular
weight, specially adapted for the physicochemical treatment of wastewater because
it contains a special molecule that facilitates the separation of the colloidal material
by flotation.
This flocculent is soluble in any type of waste water, regardless of its quality. It is
a stable product, without phase separation, having a low freezing point, compared to
regular emulsions and capable of carrying out formulations that are maintained
at extreme temperatures (<20 C). The dilution used for the treatment of leachates
is 0.3% in distilled water.
The characteristics of this flocculent are shown in Table 6.
Fig. 5 The stages of preparation of the cactus juice
Fig. 6 UV absorbance 2,250

spectrum of cactus juice
at 200 nm
Absorbance (A)
1,500
0,750
0,000
100,0 300,0 500,0 700,0 900,0
Wavelength (nm)
Juice diluted to 10% in water Raw juice
Table 6 Characteristics Appearance Milky white liquid

of the flocculent
Density 1.2 g/cm3
Himoloc Polyelectrolyte
DR3000 Viscosity <600cp
pH 3.0–4.1
Cationicity 35%
Molecular weight Average
Equipment and Materials
Jar Test
The Jar test technique is the method to evaluate the optimum for coagulation
flocculation treatment at the laboratory level before scaling up. Fig. 7 shows a device
model for performing tests at the laboratory level.
The experimental set-up used for the treatment of leachates by the laboratory-
scale physicochemical coagulation-flocculation process consists of a Jar-test device:
Model ISCO RPM/OPM (Fig. 7) in which the blades stirring were connected to
a motor that operates under adjustable conditions. The coagulation – flocculation –
was carried out using this Jar-test system according to the following steps:
pH Adjustment
Since pH is one of the most restrictive parameters of the coagulation step and
affects the hydrolysis equilibrium produced by the presence of the coagulating
agent, the study of the pH effect was performed at three level: a basic pH,
moderately acidic, and acidic by the addition of sulfuric acid H2SO4 38% or
sodium hydroxide 30%. The latter usually contributes to coagulation. The appro-
priate pH choice during coagulation flocculation depends on the type of coagulant
used for the study.
Coagulation
The purpose of the coagulation is to agglomerate the particles in suspension between
them and then recover them by decantation. Between these particles in suspension,
electrostatic repulsion forces are exerted that must be canceled to allow the agglom-
eration of these. These charges can be neutralized by polyvalent cations. The
purpose is to precipitate the colloidal particles by agglomerating them or by absorb-
ing them on polymers.
The addition of the coagulant thus makes it possible to suppress the repulsions
between the particles thanks to the metal cations.
After adding the coagulant selected for the study (40% FeCl3, SIWW, or Al(Cl)n),
a rapid stirring of 150 rpm for 10 min is adopted.
Flocculation and Settling

To accelerate the settling of the suspended matter, one of the two flocculants was
injected: either cactus juice or industrial flocculant (Himoloc DR3000) to promote
Fig. 7 Jar test Model ISCO RPM/OPM
the formation of floc macros. The flocculant is added with slow stirring at 30 rpm for
20 min and decantation for 30 min.
Ventilation Device
The decomposition of all organic matter (protein, lipid, or carbohydrate), consisting of a

range of products whose complexity is increasing, is the result of the life of autotrophic
and heterotrophic microorganisms, which develop spontaneously in wastewater in
anaerobic or aerobic environment. These bacteria are used as preferred substrate in the
biodegradable carbonaceous organic materials which are measured by BOD5.
Aeration is the introduction of oxygen into the leachate to feed the naturally
occurring microorganisms with the oxygen necessary for their nutrition and
multiplication.
To examine the aerobic treatment, the leachates are placed in three glass reactors
named R0, R1, and R2. The three reactors are agitated continuously until the end of
the experiment. The reactor R0 contains 10 liters of leachate without any aeration,
the reactor R1 contains 10 liters of leachate and aerated continuously, while the
reactor R2 containing 10 liters of leachate and aerated batch wise (30 min of
aeration followed by 30 min of rest). The flow rate of the aeration is 160 liters of
air per hour (Fig. 8).
The bacteriological analysis is performed once a week, while the physicochem-
ical parameters (dissolved oxygen, turbidity, COD, pH, conductivity) were analyzed
daily. The analysis of the COD is applied to samples decanted for 1 h.
Anaerobic Treatment Device Combined with Aerobic Treatment
The leachate used for the study of anaerobic treatment combined with an aerobic
treatment is stored in a 30-liter polyethylene watertight container with a screw cap
Fig. 8 Experimental device Time

for aeration controller
Diffuser
160L/h
Air pump
Leachate
Magnetic
agitator
R0 R1 R2
and washer gasket to prevent any kind of contact with air. The duration of the
anaerobic treatment is 43 days. During this period, physicochemical analyses were
done three to four times a week.
After this time, we placed 10 liters of the same leachate in another glass reactor
for aerobic treatment by the use of a pump that feeds the reactor with oxygen at a rate
of 3.5 liters per minute. The aerobic reactor is maintained on continuous agitation
throughout the period of the test (Fig. 9).
The duration of aerobic treatment is 30 days; physicochemical analyses were
carried out three to four times a week, while microbiological analyses are done only
once a week.
Measurement of Global Parameters
The pH of the solutions was measured using a pH meter “Accumet basic ab15 pH
meter” of the Fisher Scientific brand equipped with a Ag/AgCl combined glass
electrode according to standard NF T 90-008 February 2001 (T 90-008).
The Chemical Oxygen Demand (COD) was carried out according to the AFNOR
standard in force (NF T90-101 February 2001 (T90-101)).
The measurement of the Biological Oxygen Demand after 5 days (BOD5) was
facilitated by the use of the manometric method ((NF EN 1899 May 1998) (T90-103))
using BOD meter brand VELP equipped with 6 bottles of 500 ml amber glass, and the
samples are maintained at constant temperatures of 20 C and in the dark.
The wavelengths 436 nm, 540 nm, and 660 nm distributed over the entire visible
spectrum are used for the determination of the color according to standard NF EN
ISO 7887 January 1995 (T 90-034 section 3). In order to determine the absorption
maximum, one can take the entire absorption spectrum of these three wavelengths.
The typical 254 nm wavelength of the polyphenol compounds is usually chosen
for the determination of the OM, because it represents the absorption wavelength of
the conjugated systems (aromatic nuclei) (Chin et al. 1994).
The turbidity was measured according to standard NF EN ISO 7027 March 2000
(T 90-033) using a Turbidimeter-HACH model 2100 N turbidimeter.
Displacement of leachate in the aerobic reactor

after 43 days
Air pump
Threaded Diffuser
plug
Leachate
Polyethylene
can Bar
Magnetic
agitator
Anaerobic reactor Aerobic reactor
Fig. 9 Anaerobic treatment device combined with aerobic treatment
The determination of the suspended matter SM was carried out by the

centrifugation method according to the standard in force (NF T 90-105 January
1997 (T 90-105)).
Phenolic compounds were determined by the colorimetric method using the
Folin-Ciocalteu reagent (Macheix et al. 1990).
In aqueous solution, the polar method of anionic surfactants forms with methyl violet
(cationic) a complex soluble in toluene and capable of a colorimetric assay. Hundered
millilitre of diluted sample, 5 ml of buffer solution, 2 ml of methyl violet solution, and
30 ml of toluene are added to an ampoule. The toluene extract is collected in a 50 ml
flask and decanted to 50 ml with toluene and stirred gently and uniformly to prevent the
emulsion. The spectrometric reading is carried out at the wavelength of 615 nm.
The determination of nitrates was carried out by the spectrometric method in
the presence of sulfosalicylic acid according to standard NF EN ISO 78-90 January
1997 (T 90-045).
The determination of the total phosphorus was carried out by the spectrometric
method according to standard NF T 90-023 January 1997.
The determination of the NH 4 ammoniacal nitrogen was carried out by the
spectrophotometric method with indophenols blue according to the AFNOR NF T
90-015 January 1997 standard.
The determination of Kjeldahl nitrogen was carried out by the method
after selenium mineralization according to the AFNOR standard NF EN 25663
ISO5663 January 1994 (T90-110).
The main heavy metals studied are copper, zinc, chromium, nickel, lead, anti-
mony, and tin being the most frequently found in leachates of household waste. The
heavy metals were analyzed after mineralization by plasma torch (CNRST Rabat).
Experimental Design
A central composite rotatable design for k independent variables was employed to

design the experiments (Box et al. 2005) in which the variance of the predicted
response, Y,^ at some points of independent variables, X, is only a function of the

distance from the point to the design center. These designs consist of a 2k factorial
(coded to the usual 1 notation) augmented by 2*k axial points ( α, 0, 0), (0, α, 0),
(0, 0, α), and 2 center points (0, 0, 0) (Goupy 2001). The value of α for rotatability
depends on the number of points in the factorial portion of the design, which
is given in Eq. (1): α = (NF)1/4 (1) where NF is the number of points in the cube
portion of the design (NF = 2k, k is the number of factors). Since there are three
factors, the NF number is equal to 23 (=8) points, while α is equal to (8)1/4 (=1.682)
according to Eq. (1). In this study, the responses were phenol removal (Yphenol), COD
removal (YCOD), BOD5 removal (YBOD5), color removal (Ycolor), and volume
decanted sludge (Yvds) of leachate of municipal solid waste. Each response
was used to develop an empirical model that correlated the response to
the coagulation processes activated variables using a second-degree polynomial
equation as given by Eq. (2) (Louvet and Delplanque 2005): Y ^ ¼ βo þ β 1 X 1 þ β 2
X2 þ β3 X3 þ β12 X1 X2 þ β13 X1 X3 þ β23 X2 X3 þ β11 X12 þ β22 X22 þ β33 X32 (2)
where βo the constant coefficient, βi the linear coefficients, βij the cross-product
coefficients, and βii the quadratic coefficients.
The software JMP ® 10 was used for the experimental design, data analysis,
model building, and graph plotting.
Results
Characterization of Raw Leachate
The characterization of the leachates L1, L2, L3, and L4 from municipal solid waste
of Mohammedia city is illustrated in Table 7.
The characteristics of a leachate can generally be represented in terms of basic
parameters such as COD, BOD5, BOD5/COD ratio, color, pH, and metal content
(Kjeldsen et al. 2002). The results obtained show that the leachate is characterized by
a pH between 3 and 4. These values characterize leachates very young or contam-
inated by industrial waste. The pH value of the leachate releases is a function of
several parameters, in particular the leachate storage time, characteristics of the
waste collected, and the leachate discharge sampling period (Assou et al. 2015.
The results obtained showed that the leachate selected for the study is character-
ized by high concentrations of organic matter and high concentrations of ammonium
and nitrogen compounds. The leachates studied are characterized by a putrid and
unpleasant odor, a dark color, oscillating between yellow and dark red, which is due
to the richness of organic matter.
The measurement of the conductivity gives an overall assessment of the ions
present in the leachate mainly mineral ions and the degree of mineralization. The
conductivity values observed vary from 10,000 to 14,000 μs/cm. These values are
low when compared to an old leachate whose electrical conductivity is of the order
of 24,000 μs.cm1 due to the contribution of the highly mineralized discharge
Table 7 The characterization of the leachates from municipal solid waste

Parameters L1 L2 L3 L4
pH 3.13 3.8 3.65 4.12
Conductivity (ms.cm1) 13.84 12.07 13.4 10.54
Turbidity (NTU) 1200 1620 1850 1305
COD (mg O2.L1) 43.000 61.440 64.400 44.160
BOD5 (mg O2.L1) 21.538 28.750 30.120 25.000
BOD5/COD 0.5 0.47 0.46 0.56
Detergent (mg.L1) 610.42 512.54 416.84 414.15
Phenol (mg.L1) 14.85 71.12 56.02 60.3
Volume of decanted sludge 80 18 7.8 8
(mL.L1)
Absorbance ʎ1 = 254 nm >3; 0.2/ >3; 0.6/ >3; 0.4/ >3; 0.4/
FD = 200 FD = 200 FD = 200 FD = 200
ʎ2 = 436 nm >3; 0.021/ >3; 0.038/ >3; 0.027/ >3; 0.023/
FD = 200 FD = 200 FD = 200 FD = 200
ʎ3 = 540 nm >3; 0.016/ >3; 0.028/ >3; 0.02/ >3; 0.018/
FD = 200 FD = 200 FD = 200 FD = 200
ʎ4 = 660 nm >3; 0.017/ 3 >3; 0.022/ >3; 0.019/
FD = 200 FD = 200 FD = 200
Suspended matter (g.L1) 21.61 10.87 7.22 7.65
SO42 (μg.L1) 161 181 124 156
Total phosphorus 1700 1580 2320 1880
(mg P.L1)
Orthophosphate 0.35 0.41 0.27 0.30
(mg P.L1)
Nitrates (mg N. L 1) 860 780 910 650
NH4+ (mg.L1) – – – 200
NTK (mg.L1) – – – 1290
Cu (mg.L1) – – – 1.03
Zn (mg.L1) – – – 1.45
Cr (mg.L1) – – – 2.5
Ni (mg.L1) – – – 0.27
Pb (mg.L1) – – – 0.53
Sb (mg.L1) – – – 0.9
Sn (mg.L1) – – – 0.6
Heterotrophic bacteria – – – 7.5
(log(10) UFC/ml)
leachate. In addition, the observed values of turbidity vary between 1850 and 1200
NTU. These values characterize young leachates with a high content of colloidal
matter and suspended matter. The latter (SM) varies between 21.61 and 7.22 g/l.
Turbidity and conductivity score very high values far exceeding the standards of
treated wastewater. Chemical oxygen demand accounts for most of the organic
compounds and oxidizable mineral salts (Makhoukh et al. 2011). The COD values
observed in this study range from 43,000 to 64,000 mg O2/l. The lowest
concentration is observed for the leachate L1. A high COD value greater than
64,000 mg O2/l was observed for L3 leachate, indicating high organic load associ-
ated with these very young leachates in the acetogenesis phase, while high concen-
trations of ammonia nitrogen (200 mg/l) and NTK (1290 mg/l) were detected. The
concentrations of ammoniacal nitrogen detected remain high compared to the results
detected in the leachates studied by Idlahcen et al. (2014).
The biological oxygen demand, which is an indicator of organic water pollution,
expresses the level of biodegradability of the effluent (Makhoukh et al. 2011). The
four leachates (L1, L2, L3, and L4) had BOD5 ranged from 30 to 21,000 mg O2/l.
The lowest value is observed for leachate L1, and the highest value is observed for
the leachate L3, which shows a correlation between the COD and the BOD5.
Kjeldsen et al. (2002) showed that the BOD5 leachate studied had values up to
81,000 mg/l for fresh leachate samples and only 4200 mg/l for old leachate samples.
The BOD5/COD ratio is a good indicator of the biodegradability of an effluent.
A BOD5/COD ratio of less than 0.1 indicates low biodegradability. A BOD5/COD
ratio greater than 0.3 indicates significant biodegradability. Mean leachate character-
ization indicated a BOD5/COD ratio of around 0.5 which shows that the leachate is
rich in biodegradable organic matter. Souabi et al. (2010) showed that for releases of
Mohammedia leachate (stabilized leachates) the COD/BOD5 ratio varies between
5 and 7.5, showing that the leachate is not easily biodegradable (rich in humic and
fulvic substances) and can therefore cause several impacts on surface waters (Oued El
Maleh). The same authors have shown that the COD values obtained vary between
2301 and 2750 mg/l and remain much lower than the content detected by Navarro and
Veron (1992) discharged at sea. According to Courant and Aimar (1996), the BOD5/
COD ratio, which indicates the biodegradable character of carbon pollution, is of the
order of 0.5 for young leachates and decreases to 0 for stabilized leachates.
The results of leachates obtained showed significant absorbances at 254 nm,
which is composed of phenolic compounds present in the leachate, the measurement
of which sometimes requires significant dilutions (up to 200 times). The absorbances
measured at 254 nm remain very important, which shows that the leachates are
rich in phenolic substances. The leachate coloration is produced by the organic
material; the distribution of the MO was determined by UV absorbance measurement
at 254 nm.
Characterization of Settled Leachate
For the study of the effect of decantation without any prior treatment, one liter
of leachate from municipal solid waste was transferred in a graduated glass test
tube or in cones to be decanted. Leachate is left decanted overnight (24 h).
Different parameters were analyzed on decanted leachate. Table 8 illustrates the
parameters analyzed:
Decantation is a mechanical separation operation, by difference in gravity of
immiscible phases of which at least one is liquid. It is possible to separate liquid
phases, a solid phase suspended in a liquid phase.
Table 8 Characterization of decanted leachate for 24 h

Removal efficiency by the settling
Parameter Decanted leachate effect (%)
pH 5.6 –
O2 (mg/l) 0.52 –
Temperature ( C) 23 –
Conductivity (ms.cm1) 10.64 –
Turbidity (NTU) 980 47
DCO (mg O2.L1) 40.500 37
DBO5 (mg O2.L1) 20.200 33
DBO5/DCO 0.5 –
Detergent (mg.L1) 340 18
Phenol (mg.L1) 15 73
Volume of decanted sludge 116 –
(mL.L1)
Absorbance ʎ1 = 254 nm >3; 0.2/FD = 200 50
ʎ2 = 436 nm >3; 0.020/ 26
FD = 200
ʎ3 = 540 nm >3; 0.014/ 30
FD = 200
ʎ4 = 660 nm >3; 0.015/ 32
FD = 200
Suspended matter (g.L1) 3 58
Total phosphorus (mg P.L1) 1300 44
Nitrates (mg N. L1) 520 43
NH4 (mg.L1) 120 40
If a solid suspension is allowed to stand in a liquid phase, it is observed that

the particles under the action of gravity and buoyancy of Archimedes tend to fall to
the bottom or to rise to the surface according to their density and size. This settling
can however be relatively slow for very fine particles (sensitive to thermal agitation)
and particularly viscous liquids.
Table 8 shows the characterization of decanted leachate for 24 h. For decanted
leachate, the pH of the effluent varies around 5.6, while the value of the conductivity
obtained is 10.64 ms/cm remains lower than that detected in the case of raw leachate.
In addition, the COD value is 40,500 mg/l. These results show that the pollutant
load generated by the leachate and reflected on the value of COD depends on the
composition and the nature of the compacted waste often producing discharges of
leachates rich in easily settled organic matter. In addition, the detected phenol
concentration admits as a value 15 mg/l which is much lower than that detected in
the raw leachate with a yield by simple decantation of 73%. The detergent concen-
tration is 340 mg/l with a lower detergent removal efficiency (18%), which causes
foams to disturb the aquatic environment if leachate effluents are not treated. The
value of the BOD5 is 20,200 mg O2/l, for a BOD5/COD ratio greater than 0.3
indicates a significant biodegradability which justifies that the leachate is young.
Assou et al. (2015) showed that decantation of leachate releases significantly reduces
leachate pollution (approximately 30% COD).
The low concentration of dissolved oxygen (O2 = 0.52 mg/l) in decanted
leachate indicates that the anaerobiosis phenomenon is predominant. Indeed, oxygen
is highly stressed for the degradation of organic matter and the oxidation of
minerals present in the effluent during aerobic degradation. In addition, the recorded
temperature is 23.2 C; this value will be favorable to the maintenance of colonies
of “mesophilic” microorganisms that develop at a temperature between 20 C and
40 C (Kouamé 2007).
Staining is high for decant leachate due to high turbidity and very high Suspended
Matter content. The leachate examined contains high levels of mineral and organic
matter. Significant levels of nitrogen compounds, total phosphorus, phenols, and
detergents were also detected.
Application of Composite Plans for the Treatment of Leachate

of MSW
As a first approach, the experimental design can be conceived as a means of

knowing which factors or interactions have a statistically significant influence on
the response studied.
For the leachate treatment by the coagulation flocculation process, it is known in
several cases that the pH, the concentration of the coagulant, and the concentration of
the flocculant have an influence on the elimination of the pollution. These are the
three factors chosen for this study.
The obtained model can only be used within the field of study, hence the
usefulness of a correct preliminary study. The preliminary study allowed us to
choose a pH range between 5 and 7, a coagulant dose range between 32 and
48 ml/l equivalent to 9.44 and 14.16 g/l, and a flocculant dose range between
8 and 16 ml/l. Table 9 shows the values of the coded (Xi) and natural variables
(Xj) obtained after the preliminary study which make it possible to define the whole
of the experimental domain.
The step of variation (Δxi) is the range between two successive natural variables,
divided by that of the coded variables. The steps of variation for each of the factors
are collected in the same previous table relating to the experimental domain of the
chosen factors.
Table 9 Experimental domain of selected factors

Variables (Xj) Unite Coded variables: X1, X2, X3*
a – 0 + A
X1 = pH – 4.31 5 6 7 7.68
X2 = coagulant dosage g/l 7.82 9.44 11.8 14.16 15.75
X3 = flocculent dosage ml/l 5.3 8 12 16 18.7
An experimental design is elaborated in this study, whose input factors present a

large number of levels; it is a centered composite plan. In order to obtain a good
descriptive quality of the model and to allow a reliable prediction in all the exper-
imental domain considered for a reasonable number of tests, we realized the matrix
of experiments of the Composite Centered Design with the rotation isovariance
(Louvet and Delplanque 2005; Khoder 2011; Anouzla 2014) shown in Table 10.
All the tests carried out and the results obtained in terms of reduction of COD,
BOD5, color, turbidity, phenol, and variations in the conductivity (ms/cm) and
sludge produced (ml/l) are grouped in Table 11.
Exploitation of experimental results is often quite fast. The principle of exploitation
is simple: it consists in calculating the coefficients of the polynomial model; the higher
the absolute value of the coefficient, the more the corresponding term (simple factor or
interaction) will influence the response studied. The difficulty is rather to be able to
distinguish a true influence and the role of uncertainty inevitably tainting any measure.
Recall that a factor is significant when its value of Snedecor estimated experi-
mentally (Fexp) is greater than or equal to the value of critical Snedecor (Fc) at a
level of confidence that we have chosen a priori equal to 95%. The sign of a
parameter gives the direction of variation of the response. Indeed, when a factor
goes from level (1) to level (+1), we say that its effect is positive when its sign is
positive and that its effect is negative when its sign is negative (Louvet and
Delplanque 2005; Khoder 2011; Anouzla 2014).
Effect on the COD Removal

Table 12 summarizes the different factors influencing the removal of COD and
their meanings.
Table 10 Experimental Logical order X1 X2 X3

matrix of composite plane
1 1 1 1
centered with rotation
isovariance 2 1 1 1
3 1 1 1
4 1 1 1
5 1 1 1
6 1 1 1
7 1 1 1
8 1 1 1
9 1.68179 0 0
10 1.68179 0 0
11 0 1.68179 0
12 0 1.68179 0
13 0 0 1.68179
14 0 0 1.68179
15 0 0 0
16 0 0 0
1616
Table 11 Model configuration and answers (coagulant SIWW)

Code X1 X2 X3 COD (%) BOD5 (%) Color (%) Turbidity (%) Conductivity (ms/cm) Sludge (ml/l)
5 9.44 8 25.28 61.76 85.27 70.98 14.3 88
+ 5 9.44 16 15.74 57.35 84.8 75.68 14.19 68
+ 5 14.16 8 29.63 64.71 66.8 71.8 15.6 82
++ 5 14.16 16 23.11 61.03 69.47 79.5 15.8 78
+ 7 9.44 8 30.33 64.71 84.53 73.5 15.12 160
++ 7 9.44 16 44.28 72.06 87.4 73.63 15.13 126
++ 7 14.16 8 34.69 66.91 93.6 86.63 15.61 148
+++ 7 14.16 16 60.15 79.41 90.8 84.45 15.54 120
a00 4.32 11.8 12 12.51 55.88 75.4 58.93 15.02 80
A00 7.68 11.8 12 40.7 69.85 84.47 69.65 15.55 190
0a0 6 7.83 12 14.66 55.88 81.73 81.35 14.02 40
0A0 6 15.77 12 52.33 76.47 72.07 87.25 16.62 54
00a 6 11.8 5.3 41.24 70.59 82.67 80.5 15.06 75
00A 6 11.8 18.7 48.67 73.53 86.53 80.5 15.22 36
0 6 11.8 12 52.92 76.47 73.33 80.05 15.77 40
0 6 11.8 12 52.75 76.47 68 80.35 15.55 41
M. Abouri et al.
Table 12 Effects tests for COD removal
Source of Degree of Sum of F-Value c Rapport t p-Value d

variation freedom a squares b
X1(5,7) 1 1109.59 35.03 5.92 0.0010e
X2(32,48) 1 665.06 20.99 4.58 0.0038e
X3(8,16) 1 94.08 2.97 1.72 0.1356
X1*X2 1 9.05 0.28 0.53 0.6121
X1*X3 1 384.61 12.14 3.48 0.0131e
X2*X3 1 26.39 0.83 0.91 0.3965
X12 1 838.75 26.48 − 5.15 0.0021e
X22 1 464.26 14.66 − 3.83 0.0087e
X32 1 84.90 2.68 − 1.64 0.1527
a
Degrees of freedom: an estimate of the number of independent categories in a particular statistical
analysis or experiment
b
Sum of squares: the sum of the squares is a mathematical approach to determine the dispersion of
the data points. The sum of the squares is used as a mathematical means to find the function that best
suits (varies less) from the data
c
F-value: The Fisher test, or F-test, is a statistical hypothesis test that tests the equality of two
variances by reporting the two variances and verifying that this ratio does not exceed a certain
theoretical value that we look for in the Fisher table (or Snedecor table). If F is greater than the
theoretical value, we reject the hypothesis of equality of the two variances
d
p-value is the probability of getting the same (or even more extreme) value of the test if the null
hypothesis was true. The usual procedure is to compare the p-value with a previously defined
threshold (traditionally 5%). If the p-value is below this threshold, the null hypothesis is rejected in
favor of the alternative hypothesis, and the test result is declared “statistically significant”
(Wasserman 2004). In the opposite case, if the p-value is greater than the threshold, the null
hypothesis is not rejected, and nothing can be concluded about the hypotheses formulated
e
Significant at the 95% confidence level
Table 12 shows that the two factors: pH and coagulant concentration are signif-
icant for a threshold of 5%, that is, for a 95% confidence level. pH and coagulant
dosage are also significant at 95%. These two factors and the interaction between
them have an effect on the reduction of COD. On the other hand, the flocculant
dosage has no effect since the value P is greater than 0.05. The purpose of this
statistical test is to know if there are coefficients that are not influential, that is, to say
that have no effect on each of the responses. In the case where one or more
noninfluential coefficients exist on all the answers, they can be removed from the
mathematical model in order to simplify it and improve its quality.
Equation of the Model:
For three factors, the realization of a complete 5-level factor plan requires
53 = 125 experiments. While the composite plane centered with rotation isovariance
only requires 16 experiments. If only second-order interactions are taken into
account, the percentage of reduction in COD will be represented by the following
polynomial model (Jacques 1999; Anouzla 2014):
X
3 X
3 X
3 X
3
^
y ¼ b0 þ bj X j þ bjj0 Xj Xj0 þ bjj Xj 2
0 0
j¼1 j¼1j ¼1 j6¼j j¼1
This model comprises 10 terms: a constant term, three linear terms, three square
terms, and three rectangular terms. With:
^
y: Answer function
b0: Constant term of the model
bj: Coefficients of the model of the variable Xj
bjj: Coefficients of the model of the square variable Xj
bjj0 : Coefficients of the model of interaction between the variables Xj, between Xj
The gross equation for the percent COD reduction of leachate rejection with
SIWW coagulant is as follows:
%DCOØliminØ ¼ 52:93 þ 9:01X1 þ 6:98X2 þ 2:62X3 9:51X1 2

7:08X2 2 3:03X3 2 þ 1:06X1 X2 þ 6:93X1 X3 þ 1:82X2 X3 (1)
The evolution of the percentage of reduction of the COD during the leachate treatment
by the SIWW according to the volume of the coagulant and the pH of the medium to
12 ml/l of the flocculant Hymoloc DR3000, as well as the graph of the percentages of
COD observed according to the predicted percentages, are defined in Fig. 10.
The response surface materializes the regression surface from a graph in a three-
dimensional space. The graphical of the model equation makes it possible to
illustrate the variations of the response and to identify an area of the experimental
domain in which the response is interesting (Bakraouy et al. 2016). From the
response surface graph, it is noted that the increase in COD reduction is according
with increasing pH and coagulant dosage until an optimal of pH = 6 and coagulant
concentration = 11.8 g/l.
The mathematical analysis consists of estimating, by means of the least squares
method, the model coefficients p, and the N residues, namely, the differences
Fig. 10 COD observed according to predicted COD and 3D surfac6&e profiler at 12 ml/l
of flocculant
between the measured (or simulated) values and the values predicted by the model
for each of the experimental designs treatments.
The coefficient R2 reflects the contribution of the model in the restitution of the
variation of the observed response. By definition, the coefficient of determination
belongs to the interval [0, 1]. In the presence of several explanatory variables, which
is generally the case in the analysis of the test results, it is imperative to avoid using
the coefficient of determination R2 to estimate the descriptive quality of the model. It
is necessary to use the adjusted (adjusted coefficient of determination R2). If the
number of experiments is equal to the number of unknowns in the system, the
coefficient R2 will always be equal to 1. It is to avoid this that the adjusted coefficient
of determination R2 has been introduced. This coefficient is defined as the difference
in 1 of the ratio between the mean square of the deviations of the residuals and the
average square of the experimental deviations. The closer the adjusted R2 and R2
values are to 100%, the better the descriptive quality of the model (Khoder 2011).
From Fig. 10 it is observed that R2 = 0.945205. The adjusted square R equals
0.863012; these two values are close to 1.
Effect on BOD5 Removal

From Table 13, we find that the pH, the coagulant dose, and the interaction between
the coagulant dose and that of the flocculant are significant for the removal of BOD5.
Fig. 11 presents the graph of percentages of BOD5 observed as a function of the
predicted percentages, and the graph of the percentage change in BOD5 during
leachate treatment by SIWW as a function of the concentration of the coagulant
and the pH of the medium, at 12 ml/l of Hocoloc DR3000 flocculant. It can be
seen that the actual values were distributed near the straight line, indicating that the
model matched the measured values. As a result, this plot showed a sufficient
agreement between the observed values of eliminated BOD5 and the values obtained
from the model.
Analysis of the results obtained in Fig. 11 shows that the reduction of BOD5 is
due to the increase in pH and the coagulant dosage. At a pH equal to 6, a coagulant
Table 13 Effects tests for BOD5 removal
Source of Degree of Sum of Value F Rapport t Value p

variation freedom squares
X1(5,7) 1 279.06621 27.3179 5.23 0.0020*
X2(32,48) 1 189.02336 18.5036 4.30 0.0051*
X3(8,16) 1 20.43218 2.0001 1.41 0.2070
X1*X2 1 1.06580 0.1043 0.32 0.7577
X1*X3 1 97.58045 9.5522 3.09 0.0214*
X2*X3 1 4.32180 0.4231 0.65 0.5395
X12 1 135.58152 13.2721 -4.68 0.0108*
X22 1 104.51114 10.2306 -3.57 0.0186*
X32 1 25.78362 2.5240 -1.59 0.1632
Fig. 11 BOD5 observed according to the predicted BOD5 and 3D surface profiler at 12 ml/l of
flocculant
concentration equal to 40 ml/l and a flocculant concentration equal to 12 ml/l; the

percentage of removal of BOD5 can reach 78.5%.
A very good correlation between BOD5 observed as a function of the predicted
BOD5 and 3D surface profiler at 12 ml/l of flocculant was obtained.
The gross equation of the BOD5 reduction percentage is written as follows:
%DBO5ØliminØ ¼ 76:51 þ 4:52X1 þ 3:72X2

þ 1:22X3 4:92X1 2 3:75X2 2 1:67X3 2 þ 0:36X1 X2 (2)
þ 3:49X1 X3 þ 0:73X2 X3
Effect on the Turbidity Removal

Variance analysis allows us to see if the variables selected for modeling have a
significant effect on the response as a whole. The results of this analysis are
summarized in Table 14. We find that the linear coefficients X1 and X2 as well as
the cubic coefficients (coagulant and pH interaction) are significant for a threshold of
5%, which is to say for a 95% confidence level.
Indeed, it is found that the pH and the dose of coagulant are factors influ-
encing the elimination of turbidity. The regression is significant at a 95% confi-
dence level.
The quality of the model fit for turbidity removal was evaluated by the deter-
mination coefficient R2 = 0.9696. The 96.96% change observed for turbidity
removal was attributed to the selected variables (pH, coagulant, and flocculant
assays), while the model did not explain 3.04% of the variations (Abouri et al.
2014).
Another way to evaluate the quality of the model fit is to plot the exp-
erimental values against the predicted values for turbidity removal. Fig. 12
shows these plots. As can be seen, the model represents the experimental data
on the studied range. The graph shows the best fit as it can also be observed by the
regression coefficient. Fig. 12 also shows 3D response surface for the elimination
Table 14 Effects tests for turbidity removal
Source of Degree of Sum of Value F Rapport t Value p

variation freedom squares
X1(5,7) 1 107.29176 26.7815 5.18 0.0021*
X2(32,48) 1 108.60617 27.1096 5.21 0.0020*
X3(8,16) 1 7.84386 1.9579 1.40 0.2113
X1*X2 1 46.60951 11.6344 3.41 0.0143*
X1*X3 1 26.10031 6.5150 -2.55 0.0433*
X2*X3 1 0.05951 0.0149 0.12 0.9070
X12 1 444.55745 110.9678 -8.24 <0.0001*
X22 1 26.18743 6.5367 2.52 0.0431*
X32 1 0.91071 0.2273 0.48 0.6504
Fig. 12 Turbidity observed according to predicted turbidity and 3D surface profiler at 12 ml/l of
flocculant
of turbidity. The best results for the removal of turbidity were obtained at very high
coagulant doses and at a near neutral pH as can be observed by the stool form at a
flocculant dosage set at 12 ml/l.
The gross equation for percent turbidity removal is as follows:
%Turbidityremoval ¼ 80:11 þ 2:80X1 þ 2:82X2 þ 0:76X3 5:42X1 2

þ 1:66X2 2 þ 0:31X3 2 þ 2:41X1 X2 1:81X1 X3 (3)
þ 0:086X2 X3
Effect on the Color Removal

The quality of the fit of the model for color removal was evaluated by the regression
coefficient R2 = 0.93.
Fig. 13 shows the experimental values compared to the predicted values for
color removal. The evolution of the percentage of color reduction during leachate
Fig. 13 Color observed according to predicted color and 3D surface profiler at 12 ml/l of flocculant
Table 15 Validation of the models

Coagulant SIWW
DCO (%) Turbidity (%) Phenol (%) Sludge (ml/l)
Optimum Xi pH = 6; SIWW = 11.8 g/l; Flocculant = 12 ml/l
Predicted response (%) 53 80 89 38
Experimental response (%) 48.5 75 83 37
treatment by the SIWW as a function of the volume of the coagulant and the pH
of the medium at 12 ml/l of Hymoloc DR3000 flocculant is also represented in the
same figure.
The ANOVA tables given by the model showed that the factors influencing the
elimination of color, the variation of the conductivity, and the production of sludge
are the pH, the coagulant dose, and the flocculant dose.
The regression coefficients for conductivity and sludge production are 0.95 and
0.92, respectively.
The gross equation for the percent reduction in color is as follows:
%Colorremoval ¼ 70:49 þ 4:78X1 2:75X2 þ 0:64X3 þ 3:69X1 2 þ 2:61X2 2

þ 5:34X3 2 þ 5:78X1 X2 0:27X1 X3 0:32X2 X3 (4)
In order to validate the models, additional experiments were carried out under the
conditions found by the models and which represent the optimal of the factors for a
maximum elimination of the turbidity, COD and BOD5.
The responses are shown in Table 15 with the values estimated by the models.
Validation is to ensure that the responses calculated for the experimental points
are about the same as the measured responses (Britel 2007; Chaudhari and Murthy
2010). The study showed that the experimental results were quite similar to the
results predicted by the model. Therefore, it can be concluded that the models
represent exactly the COD content, BOD5, and turbidity removed over the experi-
mental range studied.
The validation of this model shows that the optimal values of the factors were:
pH = 6; 12 g/l of coagulant; and 12 ml/l of flocculant. The optimal dose of a
coagulant or flocculant is defined as the value beyond which there is no significant
difference in the improvement of the effectiveness of the elimination of the pollution
after another addition of coagulant or flocculant.
Biological Treatment of Leachate from MSW
Anaerobic Treatment Combined with Aerobic Treatment

A major problem generally associated with landfill disposal is groundwater and
surface water pollution. The leachate of municipal solid waste is generally rich in
organic and inorganic pollutants, in particular phenolic compounds, suspended
solids, and other harmful substances, in particular ammonium ions, which cause
problems of environmental pollution.
The treatment of leachates of high organic load anaerobically for 43 days
followed by intensive aeration at 3.5 L of air per minute in 10 liters of leachate
over a period of 30 days yielded variable results depending on the importance of the
pollutant load and the nature of the inorganic constituents. According to the results
obtained in this work, we can conclude that the leachate of municipal solid waste of
the city of Mohammedia is loaded by the easily biodegradable organic matter.
Biological treatment by anaerobic process followed by aeration of the leachate has
given remarkable results in terms of reduction of pollution. COD, BOD5, and
turbidity removal percentages were 75%, 66%, and 60%, respectively, after
73 days with initial concentrations of 58,880 mg/l, 24,000 mg/l, and 2036 NTU
for COD, BOD5, and turbidity, respectively (Abouri et al. 2016a).
Young leachate rich in organic matter easily biodegradable promotes the develop-
ment of a bacterial flora at the expense of organic pollutants. Under ideal conditions of
aeration, these microorganisms multiply and agglomerate into small flakes that settle
when the aeration is stopped. Indeed, bacterial flocs consisting of bacteria, inert or
mineral organic matter, maintained by a mucilaginous substance, facilitate the produc-
tion of bacterial activity. The microbial populations of these flocs are complex and can
only be defined by the main ecological groups: bacteria, fungi, protozoa, and metazoans.
The biological phenomena involved in the metabolization of organic matter are
shown in Fig. 14, which shows the changes, as a function of time, respectively, of
the purifying biomass and the remaining pollution (evaluated by BOD5) in the
presence of oxygen:
The results show that from the 1st day of aeration, the biomass in the ascending
part of the curve ending in a point of inflection at the 7th day presents a practically
linear reduction of the BOD5, related to the speed of synthesis, hence a constant rate
growth of biomass. Beyond the point of inflection, a decrease in the concentration of
substrate leads to a decrease in the rate of growth, which will gradually cancel out.
There is also a slowdown in BOD5. This phase is called slow growth.
10 20
Biomasse (log(10)UFC/ml)
15
BOD5 (g/l)
O2 (mg/l)
9
10
8
5
7 0
1 6 11 16 21 26 31
Time (day)
Biomass (log(10)CFU/ml) BOD5 (g/l) O2 (mg/l)
Fig. 14 Variations of biomass, BOD5 and O2 as a function of time
The increase in cell mass, at a given moment, is a function of both the mass of
microorganisms present and the concentration of the substrate, the biodegradability
of leachate rich in organic matter. The growth rate vanishes when the microorgan-
isms are no longer fed and the population hardly increases anymore. As more
and more organizations are fighting for the same food, it is no longer available in
sufficient quantity to allow others to enjoy it. The population tends to stabilize. After
21 days of aeration, the concentration of biomass increases thereafter. Indeed, the
development of anaerobic and aerobic biomass is a function of several parameters
such as the physicochemical characteristics of the effluents to be treated, nutrients,
dissolved oxygen, residence time, types of microorganisms, etc.
Devices used in the experiment for anaerobic treatment and aerobic treatment can
be considered effective, easy, and less expensive. Oxygen diffusers produce fine air
bubbles seem a ventilation system for the proper mixture of aerated leachate and
maintains dissolved oxygen in the effluent. This treatment also eliminated odors and
clarified leachate. In addition, it has been found that this technique has a significant
effect on the evaporation of leachates and therefore its partial elimination. It
would be recommended to treat anaerobic leachate followed by aeration of the
young municipal solid waste leachate before discharge to the receiving environment.
Therefore, leachate storage under anaerobic conditions (deep basin) is interesting
and can significantly reduce pollution.
Anaerobic treatment combined with aerobic treatment has been found to be very
effective in treating leachate from municipal solid waste and improving the biode-
gradability of leachate.
Aerobic Treatment by Continuous and Discontinuous Aeration

The results of the continuous and discontinuous aeration show a slight decrease in
the detergent concentration during the first week, a decrease in the detergent
concentration of 48 to 25 mg/l in the case of continuous aeration and 48 to
18 mg/l in the case of discontinuous aeration. In parallel, the percentage of detergent
removal in the case of a continuous aeration is 68% for a period of 12 days of
aeration, while it presents 92% for the same period in the case of aeration discon-
tinuous. In addition, there is a significant reduction in turbidity from 989 NTU
(11th day) to 678 and 756 NTU for continuous and discontinuous aeration respec-
tively and remains stable thereafter.
The results show a decrease in the concentration of COD from 45,000 mg/l to
24,000 mg/l after 28 days of continuous aeration. Throughout this period, an
optimum of COD removal of 53% is observed. In the case of discontinuous aeration,
the results showed a 44% yield of COD removal. In addition, the removal efficiency
of BOD5 is 51% in the case of continuous aeration and 39% for discontinuous
aeration (Abouri et al. 2015).
Landfill leachate is characterized by high concentrations of dissolved organic
carbon which is a highly heterogeneous mixture of non-volatile organic compounds
and substrates based on proteins, lignin, cellulose, hemicelluloses, polysaccharides
and lipids (Nanny and Ratasuk 2002). This dissolved organic matter will be chem-
ically and biologically degraded over time, mineralized and even condensed into
high molecular weight compounds (humic substances). Given the evolution of this
organic matter over time, many authors have highlighted the interest of studying this
matrix as an indicator of degradation and/or stabilization of leachate (François et al.
2006). At the same time, the presence of cellulose and hemicelluloses subjected to
the intense bacterial activity of a mass of waste could lead to the synthesis of
bacterial polyphenols precursors of HS. In contrast, biodegradation of these com-
pounds over time (Barlaz et al. 2002) would limit this humification pathway. In the
case of lack of substrate, microorganisms could also reuse previously synthesized
humic substances (Coates et al. 2002) to produce others.
On the other hand, the low decomposition of lignin in an aerobic environment
could be responsible for the low degradation yield of organic matter contained in the
leachate studied in our case (53% elimination of COD during 1 month of study).
Labanowski (2004) performed a structural analysis of the OM contained in
leachate considered stabilized. The results showed that leachate organic matter
could be presented as a mixture of elements of three distinct contributions: an
allochthonous contribution highlighting the origin of strongly degraded plant struc-
tures with mainly the presence of woody derivatives and an indigenous contribution
with the presence elements related to the life cycle of the microorganisms of the
landfill and no longer to the result of their activity (degradation).
It can be assumed that in the stabilized leachate, the fractions are derived from the
wood-type organic debris, paper, and paperboard and remaining logs are biodegrad-
able (Barlaz et al. 2002). Also, it is probable for the stabilized leachates that the
ligneous compounds are mainly at the origin of this fraction.
According to Barlaz et al. (2002), the term humic substances includes humins that
are totally insoluble regardless of the pH of the medium, humic acids (AH) that are
only soluble in alkaline medium, and fulvic acids (AF) that are soluble whatever
either the pH.
The study of the long-term fate of the landfill-specific organic material makes it
possible to evaluate the potential risks of remobilization of pollutants trapped within
the waste but also to evaluate the state of stability of leachate. This process allows
the poorly biodegradable organic material to undergo a slow metabolism leading
to the formation of complex molecules of the Humic Substances type. Humidity,
pH, temperature, etc., affect the growth of microorganisms and their development in
the environment. Knowledge of the composition of waste is an essential prerequisite
for the proper management of leachate releases. It helps with technical and organi-
zational choices, thus enabling efficiency gains and better cost control.
According to Ceçen and Aktas (2001), close to 95% of BOD5 and 50% nitrogen
was removed at the end of the treatment cycle by sequential batch reactor (SBR). It’s
a biological treatment consisting of anoxic filling and decantation of leachate
discharges mixed with urban wastewater for a sewage/leachate ratio of 1/9.
According to the same authors, the quality of biologically treated leachate mixed
with urban wastewater can be improved by filtration over powdered activated carbon
(PAC) (Ceçen and Aktas 2001).
Due to the sometimes high sulfate concentration (up to 10,000 mg SO42/l) in
landfill leachate, special attention should be paid to the effects of high sulfate
concentrations (formation of hydrogen sulfide). (Ceçen and Aktas 2001).
The solubilization of salts contained in the waste has a major influence on the
quality of the percolates produced. It is responsible for the phenomenon of stabili-
zation of waste in landfills. The two major phases of this process are anaerobic
degradation followed by aerobic degradation.
Aerobic degradation of organic substances is generally limited in time and
space: the oxygen demand required for the oxidation of waste is too great compared
to the available oxygen within the waste mass. Only the surface layers of waste
can be the seat of aerobic metabolisms (oxygen inputs from fresh waste and/or
ambient air). During this phase, the proteins are degraded into amino acids then into
usual catabolites of aerobic processes (CO2, water, nitrates, and sulfates). Carbohy-
drates are converted to CO2 and water, while fats are hydrolyzed to fatty acids and
glycerol. The latter are then degraded into volatile acids and bases and then into
simple catabolites.
The young product percolate is characterized by high values of BOD5 (typi-
cally > 10,000 mg/l), high BOD5/COD ratios (>0.7), acid pH (typically between
5 and 6), and ammonium concentrations from 500 to 1000 mg/l (Bietlot et al. 2011).
The latter comes mainly from the hydrolysis and fermentation of the protein
compounds contained in the waste.
Changes in the composition and concentrations of dissolved elements in perco-
lates are often due to the age of the landfill facility (C.E.T). Pollutant load changes in
percolates depend on the degree of stabilization of the waste and the volume of
water that has infiltrated through the surface. Contaminant levels generally reach
their maximum in the first years of operation of the landfill (within 2 or 3 years). This
trend is especially marked for organic compounds, organic pollution indicator
parameters (COD, a5, and TOC), the microbiological population, and most inorganic
ions (heavy metals, Cl, SO42). Certain specific interactions between the materials
present in the percolates and in the waste can also result in the solution of certain
pollutants. Many organic compounds, containing nitrogen, oxygen, or sulfur, can
form soluble metal complexes as ligands (or chelates) and thereby increase the total
concentration of metals in the percolates. By way of example, humic and fulvic acids
(responsible for the brownish coloration of percolates) are considered as complex

complexing ligands and play an important role in the mobilization of heavy metals
in the long term (Cd, Cu, Zn, etc.). Some inorganic ligands, such as chlorides, can
also complex heavy metals (Cu, Ni, etc.).
Conclusion
The disposal of solid waste is one of the main environmental issues in Morocco.
More than five million tons of solid wastes are generated across the country, with
a growth rate of annual waste production reaching 3%. Waste production is
accompanied by the production of young leachate rich in organic matter with a
high level of COD.
In this work, we studied the decontamination of leachate discharges by
two treatment techniques, namely, the physicochemical treatment by coagulation
flocculation using different reagents on the one hand and the biological treatment
in aerobic and anaerobic environment. Indeed, the diagnosis of leachates used
for the study (leachate produced by the solid waste of Mohammedia) has
shown that the discharges are too heavily loaded with pollutants in the form
of BOD5 and COD. Moreover, the concentration of ammonia in the leachate
greatly exceeds 1 g/l, thus giving bad odors and increasing the concentration of
NTK. As for detergents and phenols the diagnosis has shown high levels in these
elements which requires an effective treatment to reduce the levels of these
elements.
The treatment techniques was tested at the laboratory level, in particular the
effect of the pH on the leachate of municipal solid waste in the city of
Mohammedia of different polluting loads, which has shown a significant reduction
of the organic matter in the form of chemical oxygen demand (COD) and biolog-
ical oxygen demand (BOD5). Little difference was observed in the variation of the
conductivity as a function of pH. A comparative study was carried out on the
flocculation coagulation by FeCl3 40% (commercial product) and a FeCl3-rich
(SIWW) discharge produced at the Maghreb Steel industrial unit. The latter was
valued for reducing the pollution of leachate discharges used for this study. The
results obtained showed a very interesting performance as a function of pH, the
optimum for the reduction of organic pollution in the form of COD and BOD5, and
turbidity varies from one companion to another and the formation of sludge
depends the composition of leachate. The commercial 40% FeCl3 coagulant
removed 87% of the COD at a rate of 14.4 g/l FeCl3, while the SIWW coagulant
removed only 45% of the COD.
For sludge production and turbidity removal, little significant difference was
observed for 40% FeCl3 and SIWW rejection loaded with FeCl3.
The study of the elimination of the pollution of young leachate coming from the
municipal solid waste of the city Mohammedia using the technique of continuous
and discontinuous aeration was carried out in order to evaluate the effectiveness of
a biological treatment (at low cost) for this type of effluent. A total of 90-60%
removal of surfactant was obtained during discontinuous and continuous aeration,
respectively. The phenol concentration decreased from 600 to 220 mg/l which
represents 63% of the removal of phenol by aeration. This has been accompanied
by a change in pH and sludge biodegradation. Discontinuous aeration for a period
of 9 days achieves a COD and BOD removal efficiency of up to 44% and 39%
which corresponds to the removal of 20 g/l of COD and 7 g/l of BOD5,
respectively.
The treatment of leachates of high organic load anaerobically for 43 days
followed by intensive aeration at 3.5 L of air per minute in 10 l of leachate over a
period of 30 days yielded variable results depending on the importance of the
pollutant load and the nature of the inorganic constituents. According to the results
obtained in this work, we can conclude that the leachate of municipal solid waste of
the city of Mohammedia is loaded with easily biodegradable organic matter. Bio-
logical treatment by anaerobic process followed by an aerobic leachate process has
yielded remarkable results in terms of pollution reduction. COD, BOD5, and turbid-
ity removal percentages were 75%, 66%, and 60%, respectively, after 73 days with
initial concentrations of 58,880 mg/l, 24,000 mg/l, and 2036 NTU for COD, BOD5,
and turbidity, respectively.
Devices used in the experiment for anaerobic treatment and aerobic treatment
can be considered effective, easy, and less expensive. The use of oxygen diffusers
in aerobic treatment is very interesting to obtain maximum performance, efficiency
and incomparable quality of oxygenation. These diffusers significantly reduce the
costs of using pure oxygen. The best way to oxygenate the leachate is to minimize
the size of the air bubbles, the smaller the bubbles, the more effective the oxygen
transfer.
Cross-References

▶ Biostimulation and Bioaugmentation: An Alternative Strategy for Bioremediation
▶ Management of Municipal Solid Waste in Morocco: The Size Effect in the
Distribution of Combustible Components and Evaluation of the Fuel Fractions
▶ Technologies for Treatment of Colored Wastewater from Different Industries
Acknowledgments The work done in this study was funded by the Ministry of the Environment
as part of a leachate treatment project at the Kenitra City Wastewater Facility, which we warmly
thank.
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Application of Liquid Chromatography-
Mass Spectrometry for the Analysis of 66
Endocrine Disrupting Chemical
Transformation Products in Advanced
Oxidation Processes and Their Reaction
Mechanisms
Jin-Chung Sin, Sze-Mun Lam, and Abdul Rahman Mohamed

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1634
Chromatography Coupled with Mass Spectrometry for Intermediate Products Detection . . . 1638
Advanced Oxidation Processes for EDCs Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1639
Photolysis for EDCs Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1639
Photocatalysis for EDCs Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1641
Sonolysis for EDCs Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1646
Iron Catalyzed H2O2 Production for EDCs Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1648
Conclusion and Future Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1651
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1653
Abstract
Advanced oxidation processes (AOPs) have gained a great deal of attention as
they held great promise for the treatment of wastewater contaminated with
noneasily removable organic pollutants. The assessment of transformation prod-
ucts allowed the overall efficiency of AOPs to be better understood since some
transformation products possessed higher toxicity than the mother compounds.
Liquid chromatography coupled to mass spectrometry has been heavily used as
J.-C. Sin (*)

Department of Petrochemical Engineering, Faculty of Engineering and Green Technology,
Universiti Tunku Abdul Rahman, Kampar, Perak, Malaysia
e-mail: sinjc@utar.edu.my
S.-M. Lam
Department of Environmental Engineering, Faculty of Engineering and Green Technology,
A. R. Mohamed
School of Chemical Engineering, Universiti Sains Malayisia, Engineering Campus, Nibong Tebal,
Pulau Pinang, Malaysia

https://doi.org/10.1007/978-3-319-73645-7_90
1634 J.-C. Sin et al.
an analytical tool in the environmental field as it allowed the best performance in

assigning the identity of the transformation products detected. This chapter
reviews liquid chromatography-mass spectrometry for the identification of endo-
crine disrupting chemical (EDC) transformation products formed from several
AOPs such as photolysis, photocatalysis, sonolysis, and Fenton treatment. EDCs
are a group of special interest due to their ability to exert hormonal imbalance
activity and consequently caused adverse health effects in an organism or its
progeny. Data concerning to the mechanism of AOP-mediated reactions on the
EDCs degradation are also discussed in this chapter. Finally, the future prospects
of AOPs on EDCs degradation are summarized and discussed.
Keywords
Advanced oxidation process · Endocrine disrupting chemical · Degradation
intermediate · Liquid chromstography coupled to mass spectrometry
Introduction
Endocrine disrupting chemicals (EDCs) are defined as exogenous substances that

can alter the functions of the endocrine system and consequently led to adverse
health effects in an organism or its progeny or subpopulations (Avasarala et al. 2011;
Sin et al. 2012). A plethora of the EDC substances can be classified into two
categories: (1) natural hormones that are naturally present in the environment and
(2) hormones that are fabricated. Their general nomenclature and representative
examples are shown in Table 1. The classification of EDC substances is depended
on mode of their endocrine actions including (1) mimicking the action of endoge-
nous hormones, (2) antagonizing hormone receptors, (3) disrupting the hormones
synthesis, metabolism, transport, and excretion, and (4) altering natural hormone
production pathways. In addition, some EDCs have demonstrated multiple modes of
action, which can lead to deleterious effects on the earth ecosystems (Eertmans et al.
2003). Myriad examples of reproductive and developmental abnormalities related to
EDCs exposure have been revealed over the years in a broad spectrum of wildlife
including mollusks, fish, reptiles, birds, and mammals (Esplugas et al. 2007; Skinner
et al. 2011; Mennigen et al. 2017).
According to Caliman and Gavrilescu (2009), the total number of compounds
suspected of interacting with the endocrine system was approximately 38,000.
Nevertheless, there were more than 80,000 chemicals required to analyze and
investigate their endocrine actions. The EDCs are typically detected in the environ-
ment at trace concentrations (ppm to ppb), which are still extremely toxic to aquatic
biota (Sin et al. 2012). Sources by which the EDCs entered the environment mainly
from sewage treatment plant (STP) effluents although other sources such as direct
discharge, leakage from septic tanks, and run-off from agricultural lands (Laganà
et al. 2004; Liu et al. 2009; Burkhardt-Holm 2010).
Wastewater treatment plants operated with technologies such as nanofiltration,
reverse osmosis, lagoon or pond stabilization, biological treatment with chlorination,
66
Table 1 Classification of various EDC compounds with representative examples

Class Representative EDC Empirical formula Molecular weight (g/mol) Chemical structure
Steroids and natural hormones Estrone C18H24O2 270.37
17α-Ethinylestradiol C20H24O2 272.38
Estriol C18H24O3 288.38
Trendione C18H20O2 268.35

Application of Liquid Chromatography-Mass Spectrometry for the. . .
17α-Trenbolone C18H22O2 270.37
(continued)
1635
1636
Table 1 (continued)
Class Representative EDC Empirical formula Molecular weight (g/mol) Chemical structure
Polycyclic aromatic hydrocarbon (PAHs) Dibenzofuran C12H8O 168.19
Benzopyrene C20H12 252.31
Naphthalene C10H8 128.17
Phenanthrene C14H10 178.23
Phthalates Dimethyl phthalate C10H10O4 194.18
Diethyl phthalate C10H10O4 194.18
Di-n-butyl phthalate C16H22O4 278.34

J.-C. Sin et al.
66
Alkylphenols and Bisphenol A Bisphenol A C15H16O2 228.29
4-Tert-octylphenol C14H22O 206.32
Parabens Methylparaben C8H8O3 152.15
Eythlparaben C9H10O3 166.17
Benzylparaben C14H12O3 228.24
Pesticides Pentachlorophenol C6Cl5OH 266.34
o-phenylphenol C12H10O 170.21

Isoproturon C12H18N2O 206.28

1637
oxidation by permanganate (VII), combined ozone, and filtration in sewage treat-

ment plants currently are used on the elimination of EDCs (Acero et al. 2010;
Al-Rifai et al. 2011; Stalter et al. 2011; Qiang et al. 2013; Zhang et al. 2013).
However, most reported studies have shown that application of advanced oxidation
processes (AOPs) provided a high degree of EDCs degradation in a short period
of reaction time (Lau et al. 2007; Lam et al. 2013; Zhang and Li 2014; Simsek 2017).
Most importantly, AOP methods can convert the EDCs into low molecular weight
intermediate products and eventually led to mineralization to CO2 and
H2O. Furthermore, there is no tendency to produce secondary pollution in AOP
methods. Examples of AOPs applied to the oxidation of organic pollutants are
photolysis, photocatalysis, sonolysis, photo-Fenton, and Fenton oxidation.
However, many intermediate products formed during the EDCs degradation
could be more toxic than the parent compound been treated. Identifying the inter-
mediate products generated in the course of the AOPs degradation of pollutants
in water is thus gaining attention to understand the degradation pathways and the
degradability of the intermediates produced. Recently, liquid chromatography
coupled with mass spectrometry (LC-MS) has become a highly appropriated tech-
nique for by-products identification. Time-of-flight MS (TOF-MS) and hybrid
quadrupole TOF (QTOF)-MS/MS systems in combination with ultra-high perfor-
mance LC (UPLC) have also received preference in separating, monitoring, and
identifying of intermediate products generated in wastewater treatment (Gu et al.
2011; Souissi et al. 2012; Zhu et al. 2012; Sirtori et al. 2014). Hitherto, character-
ization and identification of degradation products are still challenging tasks for
researchers working in this area.
On the basis of the above consideration, this chapter provided a comprehensible
review dealing with the use of LC-MS techniques in analyzing the different degra-
dation products generated during the AOP-mediated EDCs degradation and to reveal
their possible degradation pathways.
Chromatography Coupled with Mass Spectrometry

for Intermediate Products Detection
During the EDCs degradation process, several degradation intermediates were

formed and needed identification using a proper analytical method. Identification
of these intermediates could give a further insight into the mechanism of EDCs
degradation and can assist to obtain a total picture of the degradation pathway with
their final mineralization products. The desired final mineralization products for a
complete degradation process are CO2 and H2O.
The most commonly used analytical method is the chromatography coupled with
MS (Souissi et al. 2012; Khataee et al. 2016). Gas chromatography-mass spectrom-
etry (GC-MS) has been well recognized as the “gold standard” for both identification
and quantification of nonpolar and volatile pollutants due to its high selectivity and
sensitivity (Khataee et al. 2016; Ba-Abbad et al. 2017; Huang et al. 2017). However,
its application was limited to some important problems such as the loss of analytes
66 Application of Liquid Chromatography-Mass Spectrometry for the. . . 1639
during the time-consuming derivatization process and its incompatibility with polar,
thermally unstable and nonvolatile compounds. In recent years, LC-MS has there-
fore become analytical method of choice for identifying of degradation intermediates
in aqueous solution. The LC-MS spectra can give information about the mass of the
molecule through the quasi-molecular ion (MH+). Therefore, the direct coupling of
LC and MS has developed into a powerful method to analyze the evolution and
breakdown of intermediate products in a degradation process. This coupling method
was also beneficial to separate and detect polar compounds without a derivatization
step (Medana et al. 2005). The development of ultra-high performance LC (UPLC)
equipped with sub-2-μm-particle-size reversed-phase column also provided faster
analysis duration, better resolution, reduction of matrix effects, and increase of
sensitivity. The LC and UPLC have performed with the use of mobile phase mixtures
of water-organic solvent (acetonitrile or methanol) and infrequently acidified to
enhance the ionization efficiencies of the compounds (Sin et al. 2014; Al-Hamdi
et al. 2016).
Advanced Oxidation Processes for EDCs Degradation
The AOPs has appeared as a promising method in wastewater treatment due to the
fact that they offered different possible processes for strong oxidizing hydroxyl
(•OH) radicals generation to react with organic pollutants and caused the ring
cleavage. Unlike many other radicals, •OH radicals are nonselective and therefore
readily to transform a large variety of organic pollutants into nontoxic molecu-
les to eliminate the environmental pollution (Peller et al. 2001; Patil et al. 2010;
Sin et al. 2013; Liu et al. 2016; Shen et al. 2017). With adequate reaction time and
optimum operating experimental conditions, the AOPs can mineralize the hazardous
organic pollutants to CO2, which was the most stable final product for chemical
oxidation. The common AOPs developed for destroying EDCs are photolysis,
photocatalysis, sonolysis, and Fenton oxidation. Below is an overview on different
AOPs for EDCs degradation with respect to the use of LC-MS for intermediate
products analysis.
Photolysis for EDCs Degradation
Photolytical process is dependent on the ability of the pollutant to absorb the emitted
radiation from artificial or natural light. In this method, the EDCs can react photo-
chemically by reaching an excited state via the direct absorption of radiant energy or
by •OH radicals generated from dissociation of water molecules (Vallejo et al. 2015).
Weidauer et al. (2016) investigated the photodegradation of benzotriazoles (BTs)
under sunlight irradiation (290–800 nm) at neutral pH in aqueous solution for 24 h.
With the identification of degradation intermediates via LC-QTOF-MS, a proposed
pathway of the photolysis of BTs is shown in Fig. 1. The results in their investigation
showed that the aniline (TP 1) and aminophenol (TP 2) were the initial intermediate
Fig. 1 Sunlight photolysis degradation of benzotriazoles (Adapted from Weidauer et al. 2016)
products based on the photolytic elimination of molecular N2. A slight amount of

NH4+ was also reported to form due to the mineralization of BTs. An acetate
conjugate (TP 4) was also formed after the denitrogenation by a reaction with the
acetate buffer. Finally, the aminophenol isomers were reported to convert into
dihydroxyphenazine (TP 5), 1,6-phenazinediol (TP 6) and aminoquinone (TP 3).
The formation of intermediate products was also found from the direct photolysis
of bisphenol A (BPA) under a UV-C lamp (Kondrakov et al. 2014). Their study
demonstrated two catechol derivatives (BPA catechol and 4-(2-hydroxypropan-2-yl)-
catechol were detected using LC-MS-TOF approach. They went further to describe the
detected catechol derivatives have weaker estrogenic activity compared to BPA.
Souissi et al. (2012) identified the degradation intermediates generated upon photol-
ysis of estrone (E1) under simulated UV irradiation. Nine main degradation products
for E1 were observed by LC-Q-TOF, which revealed one to three additional hydrox-
ylation preferentially located on the aromatic ring of E1. In addition, they
also observed that the phenolic structure of the photolysis by-products still maintained,
which needed a further investigation to evaluate the estrogenic risk in the environment.
Jiao et al. (2008) investigated the photolytic degradation of tetracycline
(TC) under a 500 W medium mercury lamp (λ = 365 nm, light inten-
sity = 0.53 mW/cm2). The degradation of TC improved at low initial TC concen-
tration and high solution pH. The intermediate products from TC photolysis were
identified using LC-ESI (electrospray ionization)-MS and a degradation pathway
was proposed (Fig. 2). The degradation mechanism of TC was explained via the loss
of N-methyl, amino, and hydroxyl groups. Only 15% decrease in the total organic
carbon (TOC) of the degraded solution was also reported, revealing a majority of TC
Fig. 2 Photolysis of tetracycline under UV-A irradiation (Adapted from Jiao et al. 2008)
converted into intermediate products without complete mineralization. More

recently, the degradation of microcystin-LR (MC-LR) under UV-B photolysis has
also been examined (Moon et al. 2017). Their results showed that high UVB light
intensity benefited the degradation of MC-LR. The degradation rate constants were
found to be 0.0020, 0.0043, and 0.0061 min1 for 0.47, 0.58, and 1.57 mW/cm2.
Based on LC-MS/MS analysis, the degradation mechanism of MC-LR was deter-
mined and proceeded via two processes: (1) bond cleavage and (2) intramolecular
electron arrangement by electron pair in the nitrogen atom.
Photocatalysis for EDCs Degradation
The photocatalysis process for the degradation of organic pollutants involved the use
of semiconducting materials as photocatalysts to generate active species such as
positive hole (h+), superoxide anion (O2•–) and •OH radicals. The active species were
produced based on the generation of electron (e) in the conduction band and h+ in
the valence band when the photocatalysts subjected to light irradiation. The e can
then reduce the adsorbed O2 to O2•– radicals, whereas the h+ can oxidize either the
organic pollutants directly or adsorbed H2O molecules to •OH radicals and hydrogen
cation (H+) (Weber et al. 2012; Sin et al. 2014; Chen et al. 2015; Lam et al. 2016).
Therefore, enhancing the e–h+ separation is an important consideration in photo-
catalysis to generate large amount of active species for organic pollutants
degradation.
Norfloxacin (NOR) was subjected to BiOBr/Fe2O3 photocatalysis and the deg-
radation by-products were analyzed using LC-(+ESI)-MS (Guo et al. 2017). It
was postulated that the overall photocatalytic degradation process of the organic
compounds was most likely to have been initiated by •OH radicals. Their studies
proposed several pathways of the NOR degradation and indicated eleven interme-
diate compounds produced during the course of reaction (Fig. 3). Three different
tentative pathways were postulated for the degradation of the NOR (piperazine
ring transformation, decarboxylation, and defluorination). The report also
showed that the NOR degradation started by cleavage of the piperazine ring.
The primary reaction intermediates were further decarbonylated to give some
of the amide group-bearing phenyl ring products with the loss of CO2 gas.
Further defluorination of the compounds was the possible reason that led to simpler
molecules with m/z 278 and 192.
López-Muñoz et al. (2013) carried out the degradation of aqueous isoproturon
using the TiO2 (Degussa P25) as photocatalysts. Structural information of the main
products formed during the photocatalytic reaction has been identified using
LC-ESI-TOF-MS. A detailed mechanism for the different by-products formation
has been suggested (Fig. 4). The processes partook are: (1) •OH radicals attacked on
the isopropyl chain, dimethylamine group, and the aromatic ring, generating mono-
hydroxylation (m/z 223), di-hydroxylation (m/z 239), and their oxidized products
(m/z 221 and m/z 237), (2) N-demethylation and/or demethylation on the alkyl chain
(m/z 193, 191, 165, 163, 151, 149, and 94), and (3) substitution or oxidation of NH2
groups linked to the aromatic ring (m/z 121, 95, and 124). The chromatography-mass
spectrometry was successfully employed in their study to identify intermediates that
could not be detected by other techniques.
The photocatalytic degradation and biotoxicity reduction of tetracycline (TC) was
investigated in the presence of TiO2-supported on MCM-41 as a catalyst (Zhou et al.
2017). The intermediates and the final products of degradation were tentatively
identified by the LC-(–ESI)-MS/MS technique. The results of LC-MS/MS demon-
strated 10 major intermediates, which were in a tendency to increase first and
subsequently declined with the degradation of the TC molecules. Several mass
spectra of by-products with their m/z values were reported in their paper; however,
no reaction mechanism towards the formation of various by-products was studied.
Indomethacin (IDM) was subjected to visible light in the presence of N-doped
carbon dots/g-C3N4 photocatalysts, and the degradation products were tested using
LC-MS/MS (Wang et al. 2017). It was suggested that the overall photodegradation
of the IDM was initiated by •OH radicals. LC-MS/MS studies proposed possible
pathways of IDM degradation, and inferred numerous of by-products were produced
during the photocatalytic reaction (Fig. 5). Four different mechanistic pathways were
suggested for the degradation of the IDM (cleavage of the amide bond, decarbox-
ylation of the acetic chain, addition reaction of the C2–C3 double bond, and
hydroxylation reaction of the chloro benzene ring). Furthermore, frontier electron
densities (FEDs) data of the IDM molecules were calculated to predict the reaction
sites for the radicals attack. The C19, C17, and C20 positions indicated higher
FED2HOMO + FED2LUMO values, which demonstrated the high possibility of •OH
radicals substituted reactions took place at the chloro aromatic rings. The C17, C12,
C5, C22, C16, and C2 atoms of IDM showed more positive point charge than others,
66
Fig. 3 Photocatalytic degradation of norfloxacin using BiOBr/Fe2O3 under visible light irradiation (Adapted from Guo et al. 2017)
1643
Fig. 4 Photocatalytic degradation of isoproturon over TiO2-Degussa P25 under a 150 W medium
pressure mercury lamp (Adapted from López-Muñoz et al. 2013)
66
1645
Fig. 5 Visible light photocatalytic degradation of indomethacin in the presence of N-doped carbon dots/g-C3N4 (Adapted from Wang et al. 2017)
which implied that C17, C12, C5, C22, C16, and C2 were attacked by O2• via
nucleophilic addition reactions. The prediction of potential attack positions by
reactive species based on theoretical calculations was in accordance with their
LC-MS/MS findings.
Mena et al. (2017) investigated the visible light photocatalytic ozonation to
degrade N,N-diethyl-meta-toluamide (DEET) using WO3 catalysts. The molecular
structures of the by-products were deduced by analyzing the samples with
LC-(-ESI)-QTOF-MS analysis. The parent molecule DEET showed a clear mass
signal corresponding to m/z 206. The degradation mechanism encountered steps of
mono- and poly-hydroxylation and/or oxidation, de-alkylation, and subsequently
rupturing of the benzene ring to lead the production of short-chain aliphatic organic
acids and eventually mineralized to CO2. Their mineralization efficiencies were
further confirmed by total organic carbon (TOC) removal.
Salma et al. (2016) reported an investigation on the identification of the degradation
intermediates generated by UV-C photolytic and TiO2 photodegradation in aqueous
ciprofloxacin (CIP) at different pH values (pH 3, 5, 7 and 9). An UPLC-MS/MS
method was used in their study together with high-resolution QTOF-MSA
(Duo-Spray Ion Source working in negative ion mode). The results showed that
there were (1) fluorine atom photo-substitution by an OH group at neutral and
moderately basic conditions, (2) defluorination at neutral conditions, and (3) fluorine
conservation at strongly acidic medium. They also added that high photon energy
produced by UV-C irradiation significantly improved the photodegradation of CIP in
the presence of TiO2.
Investigation on the photodegradation mechanism of phenol and the efficiency of
photocatalysis by commercial TiO2 has also been carried out (Dang et al. 2016).
A complete degradation of phenol aqueous solution was observed after 24 h of UV-C
irradiation. The intermediate products from the phenol degradation were identi-
fied using LC-MS. Two different mechanistic pathways were proposed for the phenol
degradation (Fig. 6). Their first degradation pathway suggested that phenol was
degraded via hydroxylation reaction to form catechol, benzoquinone, hydroxyhy-
droquinone, and hydroxybenzoquinone. With a further attack of the •OH radicals,
an oxidative aromatic ring-opening reaction occurred and rendered the formation of
simple hydrocarbons, followed by oxidation to CO2 and H2O. They also suggested
that 2-phenoxylcyclohexa-2,5-dienone, [1,10 -biphenyl]-4-ol, and tectoquinone were
formed by combination of two phenoxide ions in the second degradation pathway.
Sonolysis for EDCs Degradation
During the sonochemical process, •OH radicals were generated over acoustic cav-
itation that induced the hemolytic scission of H2O molecules. The acoustic cavitation
was comprised of the formation, growth, and collapse of microbubbles in water.
The microbubbles formed via the acoustic cavitation can tend to increase and
decrease its size continuously until the resonance size reached prior to its violent
collapse. The collapse of these microbubbles can generate extremely high
Fig. 6 Photocatalytic degradation of phenol in the presence of commercial TiO2 under UV-C light
irradiation (Adapted from Dang et al. 2016)
temperature (> 5000 C) and pressure (> 1000 atm) inside the bubbles. Therefore,
the EDC molecules can react with •OH radicals or be degraded by pyrolysis (Torres
et al. 2007; Chowdhury and Viraraghavan 2009; Ayoub et al. 2010). Papadopoulos
et al. (2016) identified the intermediates and degradation pathway of ethylparaben
(EP) through LC-TOF-MS analysis. A proposed sonochemical degradation pathway
of EP is shown in Fig. 7. The LC-TOF-MS analysis of EP at 8 h reaction time
showed the formation of four degradation intermediates methylparaben (MP),
3,4-dihydroxybenzoic acid (3,4-DHB), 2,4-dihydroxybenzoic acid (2,4-DHB), and
4-hydroxybenzoic acid (4-HB) appearing at 6.9 min, 1.4 min, 1.6 min, and 2.5 min,
respectively. All the above aromatic intermediates were proposed to further oxidize
through ring rupturing reactions into aliphatic intermediates via the continuous
attack of •OH and SO4•– radicals.
In another study of the paraben, Sasi et al. (2015) studied the •OH radicals-
mediated sonolytic degradation of methylparaben (MPB). The detected degradation
intermediates from the LC-QTOF-MS analysis showed that the MPB degradation
occurred via three major steps: (1) aromatic hydroxylation, (2) hydroxylation at the
ester chain, and (3) hydrolysis reaction. It was also reported from this study that the
aromatic intermediates were further oxidized through ring cleavage reactions into
lower aliphatic acids, which finally decomposed into CO2 and H2O as evidenced by
their chemical oxygen demand measurement.
Fig. 7 Sonochemical degradation of ethylparaben (Adapted from Papadopoulos et al. 2016)
Sonolysis of persistent pharmaceutical carbamazepine (CBZ) was also

performed, and LC-MS/MS was used in the structural characterization of the
degradation intermediates (Tran et al. 2013). The analysis of degradation interme-
diates showed that the attack of •OH radicals on CBZ led to two different degrada-
tion pathways by the formation of 10,11-epoxy CBZ and 10,11-dihyroxy CBZ.
In the first degradation pathway, 10,11-epoxy CBZ was further attacked by •OH
radicals and then formed acridine via a deamination process. In the second pathway,
10,11-dihyroxy CBZ was also attacked by •OH radicals and produced anthranilic
acid and salicylic acid. Then, the acidic intermediates were reported to convert into
aniline and benzoic acid. It was proposed that these organic compounds were finally
mineralized into CO2 and H2O.
Other EDCs such as 17β-estradiol (Ifelebuegu et al. 2014), 17α-ethinylestradiol
(Ifelebuegu et al. 2014), phenol (Entezari et al. 2003; Lesko et al. 2006), 2,4,6-
trichlorophenol (Park et al. 2011), pentachlorophenol (Park et al. 2011), tetracy-
cline (Eslami et al. 2016), bisphenol A (Torres et al. 2007, 2008), alachlor (Bagal
and Gogate 2012), and dichlorvos (Golash and Gogate 2012) have also been
successfully degraded by sonochemical treatment. The results showed that this
method can be served as an effective tertiary treatment option in wastewater
applications.
Iron Catalyzed H2O2 Production for EDCs Degradation
Among transition metals, iron has been known to be a very effective catalyst for •OH
radicals generation via Fenton process. The generally accepted mechanism of the
Fenton process suggested that the generation of •OH radicals is based on the electron
transfer between H2O2 and a homogeneous catalyst (iron) (Eq. 1). The iron can
subsequently be reacted with H2O2 to produce hydroperoxyl (HOO•) radicals
(Eq. 2). The generated •OH radicals have higher oxidation potential than the
HOO• radicals; thus, the degradation process was mainly due to the former
(Wongniramaikul et al. 2007; Tay et al. 2011; Sirtori et al. 2014).
H2 O2 þ Fe2þ ! Fe3þ þ • OH þ OH (1)
H2 O2 þ Fe3þ ! Fe2þ þ HOO • þ Hþ (2)
Marković et al. (2015) investigated the degradation of ibuprofen (IBP) in aque-

ous solution by Fe2+/H2O2 treatment. Under the experimental conditions (Fe2+,
H2O2, and IBP concentrations = 25.2, 306, and 60 mg/L, respectively), a significant
decrease of IBP concentration was observed within 1 min and reached 78% degra-
dation efficiency. The LC-MS-TOF analysis of degradation products showed that the
Fenton reaction gave four aromatic products (C9H10O2, C13H18O4, C10H12O2 and
C13H18O3) and two aliphatic products (C4H6O4 and C7H12O2) due to the powerful
oxidizing •OH radicals.
The effect of Fenton reaction on the degradation of bisphenol A (BPA) in a
novel electrical discharge plasma reactor was also reported (Dai et al. 2016).
The structures of degradation intermediates and final products were identified
using LC-QTOF-MS. Various degradation products such as bisphenol-o-quinone
(BPA12QN), 5-hydroxybisphenol A (BPA2OH), 4-hydroxyacetophenone (BPAP2),
4-[2-(4-hydroxyphenyl)propan-2-yl]-2-nitrophenol (BPA2NO2), 4,40 -propane-2,2-
diylbis(2-nitrophenol) (BPA210NO2), 5-[2-(4-hydroxy-3-nitrophenyl)propan-2-yl]-3-
nitrobenzene-1,2-diol (BPA210NO26OH), 4-[2-(4-hydroxy-3-nitrophenyl)propan-2-yl]
benzene-1,2-diol (BPA2NO210OH), and 5-[2-(4-hydroxy-3,5-dinitrophenyl)propan-2-
yl]benzene-1,2,3-triol (BPA26NO21014OH) were detected. Based on these degradation
intermediates, a possible degradation pathway of BPA was proposed in Fig. 8.
They concluded that the attack of •OH radicals on BPA hydroxyl group was the
primary pathway for the by-products formation. They also added that all the identified
degradation products have lower estrogenic activity than BPA and ultimately degraded
into CO2 as well as H2O.
Sirtori et al. (2014) identified the thiabendazole fungicide (TBZ) degradation
products in water over the Fenton treatment by LC-QTOF-MS. In their investigation,
twelve degradation products were identified and most of them can be eliminated after
15 min of reaction time. They suggested possible transformation pathway of TBZ
degradation and revealed numerous hydroxylation reaction occurred in both benz-
imidazole and thiazole rings by the •OH radicals attack (Fig. 9).
The effect of iron species has also been studied by analyzing the degradation of
amoxicillin (AMX) aqueous solution under a solar simulator (Trovó et al. 2011).
It was found that the degradation of AMX was favored over potassium ferrioxalate
complex (FeOx) compared to FeSO4. A complete oxidation of the solution over
FeOx was obtained after 5 min, while 15 min of reaction time was necessary in the
presence of FeSO4. The intermediates generated during the treatment were also
identified using LC-ESI-TOF-MS analysis, which allowed to suggest the degrada-
tion mechanism proceeded via the opening of the four-membered β-lactamic ring
and further oxidized the methyl group to aldehyde and/or hydroxylation of benzoic
Fig. 8 Degradation pathway of bisphenol A by the Fenton treatment (Adapted from Dai et al.
2016)
ring, producing intermediate products after bound cleavage between different atoms
and further oxidized to low molecular weight aliphatic compounds.
Using metoprolol (MET) as endocrine disrupting chemical, the efficiency of
photo-Fenton treatment was studied under different irradiation sources: (1) UV-C
(λ = 254 nm), (2) black blue lamps (λ = 365 nm), and (3) simulated sunlight
(Romero et al. 2016). Their results showed that the photo-Fenton using black blue
lamps gave the best degradation and mineralization efficiencies. Complete degrada-
tion of MET was obtained after 7 min of reaction time, and the corresponding
total organic carbon (TOC) removal was reported to be 81.2% after 90 min of
reaction time under the determined experimental conditions (Fe2+ = 10 mg/L and
H2O2 = 150 mg/L). Using the intermediate products detected via the ESI-MS and a
LC-MSD-TOF, their proposed degradation pathway of MET was presented where
Fig. 9 Thiabendazole degradation pathway for the Fenton treatment (Adapted from Sirtori et al.
2014)
the essential degradation was possible owing to the attack of •OH radicals (Fig. 10).
An overall toxicity reduction of treated MET solution was also observed in their
photo-Fenton process.
Conclusion and Future Trends
The increasing usage of EDCs worldwide has garnered great public concern because
of the vulnerability of humans and wildlife to numerous initiations of hormone-like
activities even in trace concentrations in surface waters. Researches have shown that
AOPs are potential technologies that widely studied and applied for degradation of
organic pollutants including EDCs. The most typically investigated AOP method for
destructing EDCs in water was semiconductor photocatalysis compared to photol-
ysis, sonolysis, and Fenton treatments. Some of research works were also found in
particularly with hybrid processes of AOPs to obtain advantages of synergistic
effects as viable solution to treat these organic compounds in aqueous solution.
Although a wide range of AOP processes have been applied, •OH radical generation
1652
Fig. 10 Degradation pathway of metoprolol by the Fenton treatment (Adapted from Romero et al. 2016)
J.-C. Sin et al.
has been recognized as a main active species for EDCs degradation. At the same
time, along with the EDCs degradation, it was crucial to develop a comprehensive
database for a myriad of intermediates and by-products formed since they can
possibly be more toxic and persistent than the parent compounds. LC-MS has
shown attractiveness as a technique used for the determination of intermediate
products of EDCs degradation owing to minimal sample preparation, ease of
separation, relatively low operating cost, and compatibility of the LC-MS system
with aqueous samples. In addition, the ionization techniques employed in the MS
can deliver data related to the mass of the parent compound and intermediate
products under analysis. Selected compounds can be further investigated using
MS/MS fragmentation for structural indications.
Despite substantial progress has been accomplished, there are several technical
points that required to be further examined. A great number of the technical papers
involved investigating the behavior of an individual component tested in much
higher concentrations than identified in the aqueous environment, while the real
EDCs occurred in mixtures of multicomponents rather than as an individual com-
ponent. In addition to target chemical analysis, research works should take account
to carry out the toxicity screening in extending the understanding of AOPs effec-
tiveness for EDCs degradation as toxicity bioassays are able to test the toxicity of
either target or unknown contaminants. For the toxicity of the degradation interme-
diates, the Microtox method using bacteria Vibrio fischeri as toxicity indicator and
the inhibition of Escherichia coli respiration can be used. At this point, the signif-
icance of degradation intermediates in point of ecotoxicological should consider in
future AOPs studies. As a final remark, it should also be noticed that recent
development and validation of suitable analytical protocols seem to be key in
reliably assuring the transformation products of EDCs that can deliver good support
to the examination of the overall performance of the treatment processes.
Cross-References
Acknowledgments This work was supported by the Universiti Tunku Abdul Rahman (UTARRF/
2016–C2/S03 and UTARRF/2017-C1/L02) and Ministry of Higher Education of Malaysia (FRGS/
1/2015/TK02/UTAR/02/2 and FRGS/1/2016/TK02/UTAR/02/1).
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Olive Mill Wastewater: Treatment and
Valorization Technologies 67
Yahia Rharrabti and Mohamed EI Yamani
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1660
OMW Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1662
Physicochemical Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1662
Biological Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1663
OMW Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1663
OMW Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1665
Physicochemical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1665
Biological Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1668
Oxidation and Advanced Oxidation Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1670
Combined Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1673
OMW Valorization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1674
Land Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1674
Biogas Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1675
Composting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1676
Extraction of Valuable Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1677
Other Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1678
Situation in Morocco . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1678
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1680
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1681
Abstract
Olive oil production industry is an important traditional agro-industry in the
Mediterranean area, with an annual production of three million tons, which
accounted for 97% of the world production. Morocco is one of the Mediterranean
countries concerned with the attractive developing production of olive oil, with an
annual production capacity of 1.5 million tons of olives and the sixth largest
Y. Rharrabti (*) · M. EI Yamani

Polydisciplinary Faculty of Taza, Taza, Morocco

https://doi.org/10.1007/978-3-319-73645-7_91
1660 Y. Rharrabti and M. EI Yamani
producer of olives after Spain, Italy, Greece, Turkey, and Tunisia. Despite the
economic importance of olive mill industry, generation of huge quantities of olive
mill wastewater (OMW) and its uncontrolled disposal create a substantial envi-
ronmental problem.
OMW are characterized by its high toxicity related to its low pH, high content
of mineral salts, and high organic load. Several treatment methods have been
proposed to search the best potential solutions, including physicochemical
methods (e.g., evaporation, coagulation, flocculation, membrane processes),
biological treatment (aerobic and anaerobic digestion), and oxidation processes
(e.g., ozonation, wet air and Fenton oxidation), but the most common method
applied has been the storage of OMW in lagoons, followed by evaporation during
summer season. The complex composition of OMW and their poor biodegrad-
ability due mainly to the presence of phenolic compounds, lipids, and organic
acids make simple treatment methods not sufficient to ensure their purification.
Many biotechnological applications have been proposed for the valorization of
these liquids that significantly reduce the environmental impact of olive mills
(e.g., composting, biogas production, and recovery of valuable compounds).
Keywords
OMW treatment · Thermal processes · Chemical processes · Membrane
processes · Anaerobic treatment · Anaerobic treatment · Oxidation processes ·
Ozonation · Wet oxidation · Fenton oxidation · OMW valorization · Land
application · Composting · Biogas production · Morocco
Introduction
The olive oil industry is an agro-industrial sector of great economic importance.

Mediterranean countries are the main producers with 97% of the total olive oil
production. Worldwide olive oil production for the crop year 2015–2016 is assessed
at 3,159,500 tons. 2,322,000 tons comes from European Union countries. The biggest
olive oil-producing country is Spain (1,401,600 t), followed by Italy (474,600 t),
Greece (320,000 t), Turkey (143,000 t), Tunisia (140,000 t), Morocco (130,000 t) then
Portugal breaking the 100,000 t barrier with 109,100 t (Fig. 1) (IOOC 2016).
Since ancient times, the oil was traditionally obtained by pressure. After the big
increase in production, the extraction of olive oil was obtained by the continuous
extraction system (Fig. 2) including a vertical and horizontal centrifugation which
separates the olive mixture in three-phase: oil, pomace, and a black liquid effluent
called olive mill wastewaters (OMW) or in two phases: oil and wet pomace. The
two-phase system uses a small amount of cold water and therefore a lower dissolu-
tion of phenolic compounds remain in the oil, but this also make it bitter.
Despite the economic importance of olive oil extraction industry especially in
the Mediterranean basin, this area is affected by pollution coming from the great
amounts generated by olive oil mills. This black liquid wastewater known as
“OMW” (which comes from the olive fruit-vegetation water, the water used for
67 Olive Mill Wastewater: Treatment and Valorization Technologies 1661
Fig. 1 Olive oil producing countries (International Olive Oil Council 2016)
Fig. 2 Three-phase (a) and two-phase (b) centrifugation systems
washing and treatment and a portion of the olive pulp and residual oil) and its
uncontrolled disposal create a substantial environmental problem. The volume of
OMW varies from 40 to 60 L for pressing method, but it ranged from 80 to 100 L for
triple phase centrifugation process per 100 kg of olives (Harwood 2000). Whereas,
OMW released by dual phase decanter are of small amounts compared to the other
systems, mainly due to the addition of very low quantities of water during the olives
crushing.
The studies conducted on the composition of OMW indicated that this effluent
contains 83–92% of water as a major part and large amounts of organic molecules,
particularly polyphenolic mixtures with different molecular weights and other
organic molecules, including nitrogen compounds, sugars, organic acids, and pectins
that increase their organic load (Amaral et al. 2008; Massadeh et al. 2008; Danellakis
et al. 2011; Ntougias et al. 2013; Bouknana et al. 2014; Mseddi et al. 2015; Alaoui
et al. 2016; El Yamani et al. 2017).
The most common practice for the management of OMW includes the use of
evaporation ponds and the subsequent discharge of solids in landfills and on soil.
However, evaporation do not contribute to the reduction of OMW toxicity, which
makes the problem is always persistent. Several other treatment options have been
investigated to search the best potential solutions, and these can be divided into four
general categories: physicochemical methods (e.g., coagulation-flocculation,
adsorption, combustion, and different membranes processes), biological methods
(e.g., aerobic and anaerobic treatment), and oxidation processes (e.g., ozonation, wet
air, and Fenton oxidation). Combined processes haves also proposed to overcome
the weaknesses of each method and to increase the processing efficiency (Adhoum
and Monser 2004; Paraskeva et al. 2006; Kapellakis et al. 2008; Coskun et al. 2010;
Sampaio et al. 2011; Di Lecce et al. 2014; Amor et al. 2015; Martins et al. 2015;
Weber et al. 2015).
The complex composition of OMW and their poor biodegradability due mainly
to the presence of phenolic compounds, lipids, and organic acids make simple
treatment methods not sufficient to ensure their purification. Moreover, treatment
of OMW requires high capital and operating cost units with limited efficiency due to
high polluting loads. Recently, several research carried out on OMW had focused on
their valorization through numerous applications (e.g., composting, use as fertilizer,
biogas production, recovery of valuable compounds) (Zenjari 2000; Capasso et al.
2002; Visioli et al. 2005; Sarris et al. 2013; Elkacmi et al. 2016; El-Abbassi et al.
2017).
This study provides updated information on research works carried out on: (i) the
composition of the OMW and their toxicity, (ii) the options proposed for their
treatment, and (iii) the possible applications of valorization.
OMW Characterization
Physicochemical Characteristics
Several studies were conducted on OMW characterization. These effluents have

a very complex and heterogeneous physicochemical composition, which varies
depending on many factors such as the variety and maturity of the olives, period
of production, climatic conditions, farming methods, region of origin, and especially
the oil extraction technology (Ben Sassi et al. 2006; El Yamani et al. 2017), among
other affecting factors such as type of olives, tillable soil, and use of pesticides or
fertilizers.
OMW are characterized generally by an intensive dark brown to black color, an

acidic character, high pollution load due to their high organic matter content, which
mainly consists of polysaccharides, sugars, polyphenols, polyalcohols, tannins,
proteins, organic acids, and lipids. Moreover, OMW contain considerable amounts
of suspended solids (Amaral et al. 2008; Massadeh et al. 2008; Danellakis et al.
2011; Ntougias et al. 2013; Bouknana et al. 2014; Mseddi et al. 2015; Alaoui et al.
2016; El Yamani et al. 2017). Besides its strong organic content, OMW contain
significant quantities of mineral salts in which the most representative elements are
potassium, phosphate, and sodium (Massadeh et al. 2008; Ntougias et al. 2013).
Recent literature data concerning the average concentrations of key physicochem-
ical constituents of OMW has been summarized in Table 1.
Biological Characteristics
Several studies were also carried out on different samples of OMW in order to
highlight the microbial diversity that could be developed in this type of effluent.
OMW microbiota is under many affecting factors such as soil and fresh water
environments, specific cultivar, cultivation, and harvesting practice (Kavroulakis
et al. 2011; Tsiamis et al. 2012).
Yeasts related to Geotrichum (G. candidum), Candida (C. membranifaciens,
C. michaelii, C. inconspicua, and C. tropicalis), Pichia (P. fermentans and P. holstii),
Rhodotorula (R. mucilaginosa), and Saccharomyces (S. cerevisiae) have been isolated
from Italian OMW (Sinigaglia et al. 2010; Bleve et al. 2011). Pichia
(P. guilliermondii–syn. Meyerozyma guilliermondii) and Candida (C. diddensiae and
C. ernobii) spp. were also the main yeast biota in OMW from Moroccan olive mills
(Ben Sassi et al. 2008). The fungal flora consists essentially of Aspergillus flavius,
Aspergillus candidus, Penicillium negricans, and Alternaria sp. (Aissam 2003).
Tsiamis et al. (2012) have reported that OMW bacterial diversity consisted of
members of Firmicutes, Actinobacteria, Alphaproteobacteria, Betaproteobacteria,
Gammaproteobacteria and Bacteroidetes. While, bacterial flora in OMW was dom-
inated by fermentative members of Bacteria, such as lactic acid (Lactobacillus and
Oenococcus spp.) and acetic acid (Acetobacter and Gluconacetobacter spp.) bacteria
(Kavroulakis et al. 2011).
Mouncif et al. (1993b) have reported the total absence of fecal bacteria in OMW.
In contrast, the presence of this kind of bacteria was confirmed by Kavroulakis et al.
(2011) and it was related to the family Prevotellaceae and the Ruminococcus-
Eubacterium Clostridium cluster.
OMW Toxicity
OMW toxicity is mainly related to the phenolic compounds’ action, which are
responsible for their black coloring and which have phytotoxic and antimicrobial
properties (Capasso et al. 1992; Casa et al. 2003; Ouzounidou and Asfi 2012).
Table 1 Physicochemical characteristics of OMW
1664
References
Parameters Units Amaral Mssadeh Danellakis Ntougias Bouknana Mseddi Alaoui El Yamani
et al. (2008) et al. (2008) et al. et al. (2013) et al. (2014) et al. (2015) et al. (2016) et al.
(2011) (2017)
PH – 5.10–5.80 nd 5.62 4.98–5.10 4.50–5.32 4.33 4.5–5.0 4.86–5.38
Conductivity mS/ nd nd 11.28 nd 13.00–42.00 15.56 14.00 9.48–11.70
cm
Chemical g O2/L 7.45–68.48 78.54–160.10 nd nd 52.00–120.00 64.00 64.00 nd
oxygen demand
Biological g O2/L 0.50–9.50 23.25–63.27 nd nd 8.50–25.00 35.00 45.00 nd
oxygen demand
(5 days)
Total solids g/L 3.13–30.22 nd 64.68 41.90–54.76 nd 70.25 23.9 nd
Total suspended g/L nd 14.21–46.19 nd nd 19.00–27.40 12.8 14.8 nd
solids
Volatile solids g/L nd nd 62.18 nd nd nd nd
Ash g/L nd nd nd nd nd nd 4.96 nd
Total phenols g/L 0.027–1.051 7.739–10.432 11.00 0.20–1.80 5.00 2.10 1.31–1.78
Total sugars g/L nd nd 41.65 nd 3.52–10.48 nd
Oil and grease g/L 2.47–62.30 nd nd nd 0.80–27.40 1.12 0.6 nd
Kjeldahl nitogen g/L 0.022–0.302 0.398–1.036 0.71 0.41–1.30 nd 0.154 nd nd
Phosphorus g/L 0.011–0.162 0.158–0.403 0.328 0.03–1.00 nd 20.10 nd nd
Potassium g/L 0.169–2.210 2.053–5.492 0.730 0.47–3.00 nd 2.40 nd nd
Sodium g/L nd 0.130–0.384 0.152 nd nd 1.40 nd nd
Magnesium g/L nd 0.038–0.63 0.114 nd nd 0.32 nd nd
Calcium g/L nd 0.276–0.757 0.284 nd nd 0.38 nd nd
Chlorides g/L nd 0.486–1.111 nd nd 23.79–142.71 nd nd 0.83–1.16
Y. Rharrabti and M. EI Yamani
Morever, DellaGreca et al. (2001) have proven the negative effects of these wastes
on soil microbial populations, on aquatic ecosystems, and even in air quality.
OMW phenolic fraction has been reported to exhibit antimicrobial activity
against some strains, which is even greater than the respective activities induced
by the individual phenolic compounds, indicating the synergistic action of OMW
phenolics (Obied et al. 2007). Concerning plants, uncontrolled OMW application
could inhibit germination of seeds (Casa et al. 2003; Mekki et al. 2006), plant
growth, and photosynthetic pigments (Ouzounidou et al. 2008).
Even though phenols are considered as the principal cause of OMW toxicity,
long-chain fatty acids and volatile acids attributed to non-phenolic related toxicity
(Ouzounidou et al. 2010). Capasso et al. (1992) demonstrated that OMW remained
phytotoxic to vegetable marrow and tomato plants even after total extraction of the
polyphenols. In addition, Hanif and El Hadrami (2009) have suggested that the low
pH and the osmotic stress caused by the presence of high Na+ and Cl concentra-
tions may play a role in OMW acute toxicity. While Karaouzas et al. (2011) have
attributed the negative effect of OMW on the aquatic fauna of fluvial ecosystems to
both high organic load and fecal contamination.
OMW Treatment
Physicochemical Methods
Thermal Processes
Evaporation is the most widely used mean for OMW management. It allows
a concentration of OMW achieved either by a manmade heat source or by a natural
source of thermal energy (air, sun). The last way for OMW evaporation (natural
evaporation) is the most practical way in the Mediterranean countries. This process
consists of the storage of OMW in the large evaporation ponds of shallow depth
where OMW remain there for several weeks or even months depending on climatic
conditions. OMW is evaporated, and at the same time, a partial biological degra-
dation of the organic matter takes place through a series of aerobic and anaerobic
fermentation processes. This simple method avoids OMW discharging into sewers
and rivers and is a relatively cheap solution. However, it requires larger area
together with production of black foul smelling sludge difficult to remove and
pollutant infiltration to ground water. Moreover, the remaining paste needs further
treatment.
To overcome natural evaporation problems, evaporator panels were used to
facilitate OMW evaporation (Fiestas Ros de Ursinos and Borja 1992). This way
has reduced the area of evaporation ponds and multiplied by 40–100 the amount of
water per m3 occupied by the soil, but odor nuisances and high-energy cost are the
main disadvantages.
Others thermal treatment methods such as combustion and pyrolysis have been
tested as a ways of OMW management and as means of recovering energy for
co-fueling the olive oil extraction plant. Combustion and pyrolysis, both are
destructive techniques with high-energy requirements and expensive equipment

needed. Pretreatment of OMW and posttreatment of the emissions of toxic sub-
stances are also required.
Chemical Processes
Several chemical treatment processes for OMW are found in the literatures.
Coagulation/flocculation is one of the most effective and used methods and remains
the least expensive compared to its performance. It consists of OMW treatment by
the use of additional chemicals in order to destabilize the suspended and colloidal
matter and form an insoluble solid that can be removed easily from the waste. Oil,
suspended solids, COD, and BOD are decreased in this way. Several researchers tested
different chemicals products; the most important are ferric and ferrous chloride, ferric
sulfate, and aluminium sulfate. Mixture of these coagulants (flocculants) and acidify-
ing of the waste with hydrochloric acid solution are also tested (Kestioglou et al.
2005). Lime treatment of OMW was also studied and corresponds to pH increase
(at about 11–12) for optimal performance (Paraskeva et al. 2006). COD, phenols, and
suspended solid removal efficiencies of 50–90% were obtained in chemical treat-
ments. The major disadvantage of this process is that there is in fact a simple transfer of
the pollution from the soluble state to the mud state; large quantities of sludge with
high pollution load are produced leading to serious disposal problems. In addition,
most organic compounds contained in OMW are difficult to precipitate.
Recently, the chemical method that has attracted attention for OMW treatment
is electrocoagulation. It is a technique for destabilizing suspended, emulsified, or
dissolved pollutants in an electrocoagulation cell by introducing an electric current
without adding a chemical coagulant. The coagulant is generated in the solution
from the conductive metal plates, commonly known as “sacrificial electrodes” often
made on aluminium or iron (Fig. 3) (Bani Salameh et al. 2015). Adhoum and Monser
(2004) have found a reduction of 76% COD, 91% phenols, and 95% color after
25 min of treatment at 75 mA/cm2. Electrocoagulation process allowed removal of
total solids and COD of about 82.5% and 47.5%, respectively at 45 mA/cm2 after
70 min by using coupled iron-aluminum electrodes (Bani Salameh et al. 2015). The
main advantages of this process are its high effectiveness in removing contaminants,
simplicity of equipment, and generation of a lower volume of sludge compared with
the classic coagulation technology (Hanafi et al. 2009).
Adsorption is another chemical process used to remove hazardous inorganics and
organic compounds, especially phenols from OMW. It is a simple and relatively
economical method widely used in the removal of pollutants. Granular activated
carbon (GAC) is the most commonly used adsorbent for removing organic pollut-
ants. Adsorption on GAC showed about 30% COD reduction and a requirement of
50 kg carbon m3 effluent (Kestioglou et al. 2005). Adsorption of the OMW onto
activated clay reduced the COD by a further 71% and the phenol content by a
maximum of 81% (Paraskeva and Diamadopoulos 2006). Al-Malah et al. (2000)
have also used activated clay for OMW treatment, reduction of 81% phenols and
71% COD was obtained. Other inexpensive minerals (i.e., clays, zeolite, etc.) can be
used for removal of color and phenol adsorption from OMW.
Fig. 3 Experiment set up of 1

electrocoagulation method: A V
(1) power supply, (2) pump,
(3) magnetic stirrer,
(4) wastewater reservoir tank,
(5) cathode, (6) anode,
6 5
(7) wastewater reservoir tank
(Bani Salameh et al. 2015)
7 rpm
Membrane Processes
Membrane processes is one of the most promising treatment processes for OMW.
They have gained a main role to seek for a viable process to treat OMW streams due
to their capability to eliminate almost all of the pollutants in the water without adding
solvents. These processes are based on the use of filtration membranes that allow
separation under the pressure gradient effect of dissolved substances according to
particle size and electrical charge.
Ultrafiltration is the widely considered membrane process, while microfiltration,
nanofiltration, and reverse osmosis also have been investigated and suggested for
OMW treatment both for organic matter reduction and for polyphenols recovery. In
addition, a separation of fats that are rejected by the membrane from salts, sugars,
and phenolic substances that pass to the permeate can also be performed, enabling
the economic exploitation of these substances. Microfiltration and ultrafiltration are
used mainly for primary treatment purposes while nanofiltration and reverse osmosis
are used for final treatment (Coskun et al. 2010).
Membranes fouling may occur very easily due to gelling substances contained
in OMW. It is the major technical drawback for the implementation of membrane
technologies, leading to a reduction of the membrane efficiency. In addition,
membrane processes are not suitable for the treatment of strong OMW because of
their limited efficiency and their high costs, which make their use especially
recommended as pretreatment steps in processes that aim at the recovery of valuable,
expensive components such as polyphenols and flavoring agents from OMW. For
the reasons stated above, some measurements, pretreatment steps, and process
combinations seem absolutely necessary before the use of these processes for
OMW treatment, as reported by many studies.
Coskun et al. (2010) investigated the OMW treatment (Turkey) by membranes
techniques; OMW were previously centrifuged, then filtered via ultrafiltration mem-
branes followed by nanofiltration, and finally reverse osmosis membranes. The
maximum COD removal efficiencies obtained at 10 bars ranged from 59.4% to
79.2% for the nanofiltration membranes, whereas about 96.2% for the reverse osmosis
membranes, respectively. Likewise, an integrated centrifugation-ultrafiltration pro-
cess was proposed by Turano et al. (2002) for the OMW treatment in Italy, reductions
of 90% COD and 80% of suspended solids concentration were achieved.
Di Lecce et al. (2014) have studied the fractionation of OMW (Italy) using a two
steps microfiltration and nanofiltration membrane process at pilot scale. Results
revealed a rejection of the nanofiltration membrane towards COD, dry matter,
phenolic compounds, and antioxidant activity greater than 97%, independent of
the volume concentration factor.
Paraskeva et al. (2007) have tested a combination of different membrane
processes for the treatment and fractionation of OMW; ultrafiltration followed by
nanofiltration and/or reverse osmosis. The recovery ratio was fixed between 80%
and 90% of the initial OMW volume, at 15–35 C operating temperature and
transmembrane pressure between 1.0 and 2.25 bar. Phenols present in the OMW
were removed to an extent exceeding 95% of the initial value following the nano-
filtration step. The concentrate obtained at this stage was very rich in phenols. Better
efficiency of the OMW treatment was achieved applying reverse osmosis after
ultrafiltration.
Biological Methods
Anaerobic Treatment
Anaerobic biological process consists of microbiological digestion of OMW in
the absence of molecular oxygen driven mostly by bacteria that converts organic
compounds into biogas (methane and carbon dioxide). It involves three major steps;
hydrolysis of complex organic compounds to their monomers which are converted to
organic acids during acidogenesis and methanogenesis, the most significant anaer-
obic stage that consist of conversion of the organic acids into biogas (methane and
carbon dioxide) (Sabbah et al. 2004).
The method is widely used and particularly advisable because of their advantages
associated to the feasibility to treat wastewaters with high organic load, low energy
requirements, low production of sludge, ability to restart easily after several months
of shut down, and generation of energy in the form of biogas (Mantzavinos and
Kalogerakis 2005). However, anaerobic processes are affected by temperature,
retention time, pH, H2 partial pressure, and the chemical composition of the
wastewater, therefore, the additions of both alkali substances to neutralize pH and
substances that are sources of nitrogen such as urea or ammonia are necessary.
Moreover, the presence of compounds, such as phenols and organic acids, toxic to
methanogens in OMW appears to be a major limitation of the anaerobic digestion
of OMW (Hamdi 1996). Two approaches are proposed to overcome this problem:
(i) the dilution of OMW to reduce phenols and organic acids concentration, (ii) the
removal of compounds that are toxic to methanogenic consortia, with a prior aerobic
treatment. The latter appears to be the most suitable.
Numerous studies using different anaerobic reactor types have been investigated.
In a recent study, OMW were digested in its original composition (100% v/v) in an
anaerobic hybrid. High concentrations (54–55 kg COD/m3), acid pH (5.0), and lack
of alkalinity and nitrogen are some OMW adverse characteristics. Loads of 8 kg
COD/m3/day provided 3.7–3.8 m3 biogas/m3/day (63–64% CH4) and 81–82% COD
removal (Sampaio et al. 2011). Raposo et al. (2004) have reported that when using
an anaerobic reactor with bentonite as support medium for hydraulic retention times
of up to 25 days and an organic loading rates range of 0.86–5.38 kg COD/m3/day,
COD reductions were up to 88.8%, and methane production was 0.31 m3
CH4/kg COD.
Bertin et al. (2004) have tried to overcome the problem of inefficiency of
the conventional contact bioreactors to remove OMW phenolic compounds
by employing an anaerobic OMW-digesting microbial consortium passively
immobilized in column reactors packed with granular activated carbon (GAC) or
“Manville” silica beads (SB). Anaerobic reactors packed with GAC and with SB
showed a marked improvement in the removal of organic matter compared with
conventional anaerobic treatment. The GAC reactor achieved 78.4% COD depletion,
90% phenol reduction, and 0.08 m3 CH4/kgCOD yield, while the SB reactor achieved
48.3% COD reduction, 50.6% phenol reduction, and 0.18 m3 CH4/kg COD yield.
Ubay and Ozturk (1997) were investigated the anaerobic treatability of OMW
using a laboratory scale upflow anaerobic sludge blanket reactor (UASBR). CODs
were varied from 15 to 22.6 g/L while retention times ranged from 0.83 to 2 days;
soluble COD removal was around 70%. A methane conversion rate of 0.35 m3 per
kg COD removed was achieved. Dilution, nutrient addition, and alkalinity adjust-
ment were required.
Aerobic Treatment
Aerobic treatment is the use of aerobic strains for the biodegradation of the organic
content of the waste. It is a commonly used technology in wastewater treatment. For
OMW, known for their high organic contain specifically phenolic compound, a prior
dilution and an acclimatization period for the microorganisms are required for the
method to be effective (Yesilada et al. 1998). Kapellakis et al. (2008), have also
reported that the process can operate efficiently only at the low concentrations of the
effluent; i.e., of the order of 1 g/L COD. A long hydraulic retention time and/or with
high recycle ratios are recommended in case of high concentrations (Paraskeva and
Diamadopoulos 2006). Therefore, aerobic processes are unsuitable for direct and
efficient treatment of OMWW. They are often used as pretreatment to increase the
efficiency of the anaerobic processes.
Many microorganisms (fungi, yeast, bacteria) have been tested in aerobic treat-
ment of OMW: Pleurotus ostreatus, Bacillus pumilus, Panus tigrinus, Yarrowia
Lipolytica, Aspergillus niger, Azotobacter chroococcum, Azotobacter vinelandii,
Aspergillus terreus, Phanerochaete chrysosporium et Pleurotus ostreatus, etc.
(Hamdi et al. 1991a, b; Kissi et al. 2001; Fadil et al. 2003). The various studies
carried out on the aerobic treatment of OMW have shown a considerable rates
removal of COD and of phytotoxic compounds were achieved. Yesilada et al.
(1998) have reported a removal of 70% COD and 93% phenols using Funalia troggi
for OMW treatment, while Coriolus versicolor allowed a reduction of 63% COD
and 90% of the phenols for an initial COD of 28.20 g O2/L. A reduction of 75–66%
of total organic carbon and total phenols, respectively, and a discoloration of about
45% after 4 days of incubation, were observed using Leutinus edodes (Vinciguerra
et al. 1995). Kissi et al. (2001) have tested OMW treatment by Phanerochaete
chrysosporium; results were reduction rates of 73% COD and 83% polyphenols with
12 days of incubation for an initial COD of 50 g O2/L. A removal of 55%, 52.5%, and
62.8% of COD was obtained with aerobic treatment of OMW by Geotrichum sp.,
Aspergillus sp., and Candida tropicalis, respectively (Fadil et al. 2003).
Tziotzios et al. (2007) have examined the capability of olive fruit bacteria to
remove COD and phenolic compounds from OMW using flasks reactors at different
dilutions (20%, 50%, and 100%). The maximum phenolic and dissolved COD
removal reached up to 82–90% for the dilutions of 20%, 50%, and 100%, in
11, 23, and 30 days, respectively.
Oxidation and Advanced Oxidation Processes
Ozonation
Ozonation is a very interesting technology for industries as it can operates at ambient
conditions. It has been successfully employed for the OMW treatment either alone or
in conjunction with other process. The method can be seen as a part of advanced
oxidation processes (AOPs) that could be used in great number of reactions with
organic and inorganic compounds given that hydroxyl radical results from the
decomposition of ozone, which is catalyzed by hydroxyl ion or initiated by the
presence of traces of other substances (Bani Salameh 2015). In fact, Ozone is
considered as a powerful oxidizing agent and effective disinfectant, able to degrade
bio-refractory organic matter by attacking selectively the double bonds of unsatu-
rated fatty acids and phenolic compounds in OMW, leading to low-molecular-weight
molecules more amenable for other treatments especially those biological
(Mantzavinos and Psillakis 2004). Ozone production requires a large amount of
electrical energy and its use can be uneconomical in wastewaters with high organic
load. Therefore, this treatment can be enhanced by the addition of hydrogen peroxide
and/or UV radiation, and even with catalysts or photo-Fenton reaction.
Several studies were investigated in order to evaluate ozone’s efficiency in
treating OMW and especially removing toxic compounds. Siorou et al. (2015)
have reported that ozonated OMW held for 0, 60, 120, 300, 420, 540 min in
a glass bubble reactor, showed a drastic reduction of OMW total phenols (almost
50%) after 300 min of ozonation with a concomitant decrease of OMW toxicity.
Abatement of 80% of phenolic content and removal of 12% COD at the steady
state were reached by ozonation treatment of OMW in a continuous reactor at pH 9,
1 ml/min of liquid flow rate and 15 g O3/m3. An integration schemes were also
tested, ultrafiltration followed by ozonation was able to reach 93 and 20% of total
phenols and COD depletion, respectively (Martins et al. 2015). Tsintavi et al. (2013)
have performed a batch ozonation experiments on OMW in a glass bubble reactor.
The results were a 57–76% reduction in total phenols and a 5–18% decrease in total
carbohydrates contained in OMW. The higher removal efficiency (91% for total
phenols and 19% for COD) was showing with ozone oxidation at initial pH value of
12, in a study carried out by Bettazzi et al. (2007).
Wet Air Oxidation

Wet air oxidation (WAO) consists of a direct and total oxidation of organic
compounds by molecular oxygen in a liquid aqueous phase, under relatively
elevated temperatures and pressures (220–320 C, 50–200 bars). This technique
was successfully applied to the treatment of different kinds of wastewaters (García
et al. 1990; Verenich et al. 2004). Nevertheless, it implies severe conditions for
operating (WAO units with high nickel content alloys, much more expensive than
common stainless steel, and large thickness, in order to support the high pressures
involved) that involved high capital costs and safety issues related to these condi-
tions. Therefore, various catalysts were introduced to mitigate the severe reaction
conditions to more amenable values (125–220 C, 5–50 bars) (Gomes et al. 2007).
The WAO process has been successfully performed in the OMW treatment, and
it has been demonstrated to be a feasible to effectively reduce the levels of contam-
ination of these effluents. In fact, the oxidation reactions turn phenolic compounds
into less toxic end products, such as carboxylic acids, carbon dioxide, or other
harmless small-molecular-weight products (Weber et al. 2015). García et al. (1990)
have achieved reductions of the total phenolic content of OMW close to 99% using
pure oxygen (partial pressure 35 bars) at temperatures around 250 C. The WAO
process catalyzed by hydrogen peroxide coupled with bioxidation for OMW was
investigated by Chakchouk et al. (1994). Oxidation was conducted between 180 C
and 200 C. WAO treatment allows a complete decoloration of the solution, a 77%
COD reduction; the remaining COD is mainly low–molecular-weight carboxylic
acids (chiefly acetic) easy for a biological post-treatment.
In a comparative study, the oxidation using air as the oxygen source of OMW
diluted with synthetic urban wastewater (1:10) has been carried out in the liquid
phase at high temperatures and pressures. A positive effect has shown of the
previous neutralization of the wastewater if compared to the oxidation conducted
at the original pH of the effluent (pH = 5.3). Removal of toxic phenolic-type
compounds is accomplished under relatively mild conditions of temperature and
pressure (453 K and 7.0 MPa total pressure). In terms of DCO depletion and final
biodegradability characteristics of the effluent, the use of free radical promoters, for
instance, hydrogen peroxide, resulted in a significant enhancement of the process.
While the use of copper oxide or platinum supported catalysts has showed not only
an improvement in the COD removal rate but also a high degree of the mineraliza-
tion of the wastewater contaminant load (Rivas et al. 2001a).
Recently, Gomes et al. (2007) have studied the suitability of catalytic wet air
oxidation for the OMW treatment, in a high-pressure reactor under an oxygen partial
pressure of 6.9 bars. The complete total organic carbon and color removal was
obtained using carbon supported platinum (1 wt.% Pt) after 8 h of reaction at 200 C.
Fenton Advanced Oxidation

Fenton process is an advanced oxidation technology based on hydroxyl radicals
generation by the decomposition of hydrogen peroxide when reacting with iron ions
(Fe2+ and/or Fe3+) acting as homogenous catalyst at acidic pH (2–4) and ambient
conditions. The iron (III) ions generated during the oxidation stage promote the
removal of other pollutants by coagulation and sedimentation (Bautista et al. 2008).
The Fenton process has variants, such as Fenton-like, photo-Fenton, and electro-
Fenton processes for enhancement. Generated Fe3+ can be also reduced by reaction
with exceeding H2O2 to form again ferrous ion and more radicals. This second
process is called Fenton-like; it is slower than Fenton reaction and allows Fe2+
regeneration in an effective cyclic mechanism. Photo-Fenton’s process is an
improvement of the classical Fenton’s reagent through the addition of ultraviolet
radiation or visible light. When, in electro-Fenton process, pollutants are destroyed
by oxidation at the anode surface and/or using the Fenton’s reagent in the bulk
(Amor et al. 2015; Hadjltaief et al. 2015; Madani et al. 2015; Pariente et al. 2015).
The main advantage of Fenton process is that the reagent components are safe to
handle and environmentally benign. The process presents some other advantages:
the reaction takes place at atmospheric pressure and at ambient temperature, hence
no energy is required to activate the hydrogen peroxide; the cost-saving due to the
use of metal iron compared to iron salts, the faster recycling of ferric iron at the iron
surface and the production of harmful byproducts, is too low compared with other
advanced oxidation processes. Nevertheless, the generation of large amount of iron
sludge created at the end of the reaction that needs further treatment and the strict
control of the pH (2.5–3.5) to guarantee a high catalytic performance are the major
weaknesses of this process (Bautista et al. 2008).
Fenton oxidation processes are very effective techniques in the removal of
various organic pollutants from wastewater such as OMW and can be used as an
effective pretreatment step to reduce toxicity. They have been extensively studied for
the OMW treatment. Amor et al. (2015) were investigated the pretreatment of OMW
with a classical Fenton method. They have been able to achieve reaching reductions
of 17.6 and 82.5% of COD and total polyphenols, respectively, at pH 3.5 after 8 h
reaction, producing an effluent suitable for anaerobic treatment. In another study
done by Madani et al. (2015), the pH, iron-salt, and hydrogen peroxide dosage were
also found to significantly affect the efficiencies of Fenton process, and acidic pH
conditions were the most effective. The process showed high efficiency of COD
(83%), total phenols (98.6%), color (77%), and aromaticity (67%) removal from
the OMW.
Different results were found in similar studies; the removal of about 65% of COD
was reached when the Fe(II) concentration is 0.5 mol/L and the reaction time is
longer than 4 h (Rivas et al. 2001b). Complete removal of phenols and COD
reductions in the range 40–60% with a 2 h reaction time at a dose of 2–3 g/L ferrous
sulfate and 3 mL of peroxide (60% w/w) (Vlyssides et al. 2004). The removal of
40% COD after 2 h of treatment remained unchanged thereafter, at lower Fe(II) and
peroxide concentrations (0.03 and 0.25 mol/L respectively), COD removals were
40% after 2 h of treatment and remained unchanged thereafter (Ahmadi et al. 2005).
Pariente et al. (2015) have tested an intensified Fenton catalytic process with a Santa
Barbara Amorphous-15 silica-supported iron oxide as catalyst (Fig. 4), nearly 99%
of phenol can be removed at 160 C in an acidic environment.
In other researches, experiments with photo-Fenton and electro-Fenton processes
were performed. The photo-Fenton reaction was less pH dependent than the Fenton
process; the phenol removal rate was 60% at pH 2 and 70% at pH 5 (Mofrad et al.
2015). Hadjltaief et al. (2015) highlighted the role of UV wavelength and indicated
that the use of both UV-C (λ = 254 nm) and UV-A (λ = 365 nm) can reach 100%
phenol degradation, but UV-C was more efficient than UV-A. Electrochemical
oxidation with a titanium-tantalum-platinum-iridium anode has also been used for
OMW treatment. It was found that the process was able to remove almost entirely the
content of phenols and the appearance of color, while, COD removals were up to
40% (Gotsi et al. 2005).
Combined Processes
Combining ozonation and aerobic treatment, Benitez et al. (1999) reported a total
COD reduction of 82.5%, a percentage higher than either of the two technologies
Fig. 4 Flowsheet of experimental installation for intensified-Fenton catalytic runs (Pariente et al.
2015)
could achieve alone, indicating that ozonation increased the biodegradability of the
OMW. When aerobic treatment preceded ozonation, COD reductions of up to 81%
were reported. A combination of biological and UV/O3 process for the OMW
treatment seems to be a serious alternative in the reduction of the COD. In particular,
biodegradation of UV/O3 pretreated OMW found to have the highest removal levels;
the percent of COD removal reaches about 91% (Lafi et al. 2009). Ultrafiltration
followed by ozonation was able to reach 93% and 20% of total phenols and COD
depletion, respectively. Moreover, this sequence led to an effluent with a BOD5/
COD ratio of about 0.55 which means that it likely can be posteriorly refined in a
municipal wastewater treatment plant (Martins et al. 2015). In a previous study,
Canepa et al. (1988) have combined ultrafiltration and reverse osmosis in a pilot
plant scheme and observed 93–99% COD reduction.
Khoufi et al. (2006) have investigated an electrochemical pretreatment step of
OMW using the electro-Fenton reaction followed by an anaerobic bio-treatment. The
electro-Fenton process removed 65.8% of the total polyphenolic compounds and
subsequently decreased the OMW toxicity from 100% to 66.9%, which resulted in
improving the performance of the anaerobic digestion. The anaerobic process
applied as post-treatment reached a loading rate of 10 g COD/L/day without any
apparent toxicity. Furthermore, in the combined process, a high overall reduction in
COD, suspended solids, polyphenols, and lipid content was achieved by the two
successive stages. Amor et al. (2015) in a study of OMW treatment applied Fenton’s
reagent followed by anaerobic digestion. This combined process has presented a
significant improvement on organic load removal, reaching COD degradations from
64% to 88%. In another research, adsorption, biological treatment, and photo-Fenton
caused decreasing phenolic contents from OMW of 48.69%, 59.40%, and 95%,
respectively. However, after the sequential treatment of the three methods was
performed, higher reduction percentages in phenolic (total 99%) and organic con-
tents (90%) were observed (Aytar et al. 2012).
The different literature methods for OMW treatment are summarized in Fig. 5.
OMW Valorization
Land Application
OMW are rich in organic content and contain a significant amount of nutrients
(sodium, phosphate and potassium) (Massadeh et al. 2008; Ntougias et al. 2013).
OMW spreading on soil can enhance its fertility and promote microbiological
activity (Sierra et al. 2007), especially for soil that have low levels of organic matter,
microbial activity, biomass, and nutrient availability.
Many researchers have applied OMW on soil. Positive effects were confirmed and
were related to high nutrients concentration, especially K, and its potential for mobiliz-
ing soil ions (Paredes et al. 1999). Cox et al. (1997) suggested OMW use to attenuate
leaching of toxic organic chemical such as herbicides (clopyralid and metamitron) in
cultivated lands, because of its ability to reduce the mobility of certain organic
Fig. 5 Treatment options for OMW
compounds in soil. Saadi et al. (2007) have reported that in addition to nutritional value
of OMW, its potential herbicidal activity and ability to induce suppression of soil-borne
plant pathogens are of extra value. Kotsou et al. (2004) have also confirmed the OMW
suppressiveness against the plant pathogen Rhizoctonia solani. Whereas, OMW appli-
cation on soil may lead to some negative effects, associated with its high mineral salt
content, acidity, lipids accumulation, organic acids, and the presence of phytotoxic
compounds, especially polyphenols (Cegarra et al. 1996; Paredes et al. 1999). This is
the reason for a limitation of any effective use of OMW as a fertilizer, therefore,
pretreatment before spreading is of great importance in order to avoid or reduce the
negative effects on crops, soils, and the environment.
Biogas Production
OMW are heavily polluted, because of their high organic load and phenols content,
and hence, it can be used as a renewable energy source for biogas production through
microbial treatment.
Anaerobic digestion has been studied extensively by many researchers to produce
energy (biogas) and to purify the OMWand thus re-use it especially in irrigation (Ergüder
et al. 2000; Sarris et al. 2013). Although anaerobic digestion of OMW is feasible for the
treatment, the presence of phenolic compounds known by their high antibacterial activity
can slow down the process, hinder removal of part of the COD, and detract from its
economic viability (Hernandez and Edyvean 2008). Therefore, pretreatment of OMW is
a prerequisite and has been able to improve the performance and behavior of the
anaerobic purification of this wastewater (Mantzavinos and Kalogerakis 2005).
Ergüder et al. (2000) have reported that treatment of 1 L of OMW by anaerobic
methods allowed production of 57.19 ( 1.5) L of methane gas. Mouncif et al.
(1993a) also studied the production of biogas by anaerobic digestion of OMW, the
rate of biogas produced was reached 207 L/kg of digested organic matter.
A maximum ethanol concentration of 52 g/L was obtained in a batch reactor,
using media enriched with glucose, with sugar concentrations up to 115 g/L (Sarris
et al. 2013). Marques (2001), studied the anaerobic digestion of OMW (83%)
with piggery effluent in an up-flow anaerobic filter. The production of biogas was
1–3 m3/m3/day (65–75% CH4).
The co-digestion of various organic wastes has also been studied. Athansoulia
et al. (2012) have investigate the use of OMW (30%) as a co-substrate with waste
activated sludge (70%) to improve biogas production (methane). The biogas
production rate reached 0.73, 0.63, 0.56 and 0.46 L biogas/L reactor/day for
hydraulic retention times of 12.3, 14, 16.4, and 19.7 day. Dareioti et al. (2009)
have examined the biodegradation of a mixture containing 55% OMW, 40% liquid
cow manure, and 5% cheese whey in a two-stage continuous stirred tank reactor
anaerobic process. The methane production rate at steady state conditions reached
1.35 0.11 l CH4/L reactor/day. Fezzani and Cheikh (2008) studied the meso-
philic anaerobic co-digestion of OMW with olive mill solid waste in a batch
digester and results showed an increase in biogas production and COD removal
efficiency from 11.17 2.5 to 30.5 2.5 L/L digester and from 44.5 3 to
83.4 2%, respectively.
Composting
Various disposal approaches have been proposed for appropriate OMW manage-
ment, leading to a number of possible recycling and valorization methods (Federici
et al. 2009). Composting is one of the main technologies of OMW recycling and it is
a of particular interest for its operational simplicity and capacity to transform OMW
into a high-quality amendment, rich in stabilized organic matter and nutrients for
plants (Altieri and Esposito 2010). It has been considered an appropriate low-cost
technology for organic waste recycling and organic fertilizer production (Ruggieri
et al. 2009). Composting is an aerobic decomposition process that degrades organic
matter over a period of weeks into a granular humus-like product which can be used
as a fertilizer or soil conditioner (Tomati et al. 1996). It proceeds through three
phases: an initial activation phase, followed by a thermophilic phase characterized
by a rapid temperature increase, and a final mesophilic phase where the organic
mixture cools down to air temperature (Ryckeboer et al. 2003).
Piperidou et al. (2000) have developed a biofertilization system, based on the

ability of Azotobacter vinelandii to grow on OMW and hence their conversion into
an organic liquid fertilizer. Different substrates were tested with OMW to produce
stable compost rich of nutrients. Tomati et al. (1995) found that a fertilizer with a
high level of humification and no phytotoxic effects was obtained by composting
OMW with wheat straw. Zenjari (2000) has studied a composting process by mixing
OMW with cellulosic waste (straw), leading to a stable compost rich in humic
substances, with a reduction of 50% and 95% of COD and total phenols, respec-
tively. The nutritional value of OMW compost has been evaluated and confirmed by
several studies. Cegarra et al. (1996) applied OMW composts to cultivate horticul-
tural and other crops and found that yields obtained with compost fertilization were
similar to, and sometimes higher than, those obtained with mineral fertilizers. Tomati
et al. (1996) also observed an enhancement of activities in the plant-soil system after
the addition of OMW composts.
Extraction of Valuable Products
OMW, known by their highly polluting organic load, are also promising source
of bioactive compounds and substances of high value and great interest. Therefore,
the development of recovery processes for these valuable substances has great
importance and are more studied. Phenolic compounds are one of the most valuable
substances that OMW can provide.
Excellent biological properties such as antioxidant, free radical scavenging,
antimicrobial, and anticarcinogenic activities of the OMW biophenols are
documented (Obied et al. 2005). Visioli et al. (2005) have indicated that phenolic
compounds, as natural dietary antioxidants, may protect the organism against oxi-
dative damage caused by oxidant agents (active oxygen, free radical, etc) that are
involved in the etiology of chronic diseases such as cancer and atherosclerosis.
Many recovery processes of these compounds have been studied: reverse osmosis,
integrated centrifugation-ultrafiltration system, photochemical degradation of phe-
nols, electrocoagulation, Bioreactor (Turano et al. 2002; Adhoum and Monser
2004).
Another group of interesting compounds that could be obtained from OMW is
soluble sugars, including the sugar alcohol or polyol called mannitol. Mannitol is used
as an exicipient in pharmacy and as anticaking and free-flow agent, lubricant, stabiliser
and thickener, and low-calorie sweetener in the food industry. Fernández-Bolaños
et al. (2004, 2006) were able to recover mannitol with a high degree of purity.
As another form of OMW valorization, Elkacmi et al. (2016) have used
a fractional crystallization technique, on one hand, to extract oleic fatty acid as a
product with a very important commercial value and, on the other hand, to produce
soap and glycerin.
Other compounds of great interest and benefits could be extracted from OMW:
Pectins and oligosaccharides (Fernández-Bolaños et al. 2004), Polymerin (Capasso
et al. 2002), etc.
Other Uses
Other ways of OMW valorization were investigated and proposed, which could be
less common but also of high interest. Several studies were reviewed that OMW can
be also used as a favorable medium for the enzymes production, which can found
applications in the pharmaceutical, detergent dairy, and other industries. Lipases
(Abrunhosa et al. 2013), laccases (Apohan and Yesilada 2011), Mn-dependent
peroxidases, and pectinases (Crognale et al. 2006) seem to be the main enzymes
obtained through a microbial (fungial) treatment.
OMW represent a nutrient substrate for the production of single cell proteins thanks
to their richness in organic matter. The production of single cell protein through aerobic
yeast culture was studied by many authors because of the facility of their cultivation and
the high protein content obtained (Gharsallah 1993). It has also demonstrated the ability
of different strains to produce exopolysaccharides (Aguilera et al. 2008), rhamnolipids
(Mercade et al. 1993) using OMW as sole nutrient and energy sources. Bioplastics
(polyhydroxyalkanoates) have also been produced using OMW as a starting medium by
using different Azotobacter strains (Cerrone et al. 2010). Recently, many researchers
tried to take advantage from the phytotoxic and antimicrobial properties of OMW by
using it in agriculture as biopesticide for crops protection (El-Abbassi et al. 2017).
The different literature options of OMW valorization are summarized in Fig. 6.
Situation in Morocco
Morocco is one of the Mediterranean countries concerned with the attractive

developing production of olive oil. The olive oil sector contributes 5% to the national
agricultural GDP. Covering an area of 922,000 hectares, the national farms have a
Fig. 6 Valorization options of OMW

total production of around 1,500,000 tons of olives. The country also produces
130,000 tons of olive oil, and ranked the sixth largest producer of olives
after Spain, Italy, Greece, Turkey, and Tunisia. In terms of exports, 17,000 tons of
olive oil can be found on international markets (IOOC 2016). The main regions
of production cover almost the entire country, except for the Atlantic coastal
strip. The main variety produced is the “Moroccan Picholine” up to 96% of
plantations.
The olive oil processing sector is formed from both traditional, semi, and modern
units. The traditional segment comprises 16,000 olive oil mills with the capacity to
crush some 170,000 t of olives per year. Oil extraction rates are low, barely
exceeding 14%. The modern and semi-modern segment is made up of 334 facilities
equipped with an aggregate capacity of roughly 530,000 t of olives per year, and
with substantial room for increase (IOOC 2012). Olive oil extraction using the
traditional press and semi and modern methods (three phases and two-phase
decanter) results in the production of large amount of highly contaminated OMW.
The annual production of olive mill wastewater (OMW) in Morocco exceeds
250,000 m3 (Hanafi et al. 2010).
Many researches are also carried out on Moroccan OMW. They confirmed the
founding in studies performed in other countries. OMW is one of the strongest
industrial effluents, characterized by a low pH, high organic load (explained by
high values of DCO and DBO), great amount of total solids and a strong
concentration of recalcitrant compounds such as phenols (the most toxic com-
pounds), lignins and tannins which give it a characteristic dark colour (Ben Sassi
et al. 2006; Bouknana et al. 2014; El Yamani et al. 2017). Concerning the
microbial diversity in Moroccan OMW, Yeast and fungi populations appear to
be high in OMW than bacteria. These microorganisms support the high salinity
and acidic pH and are more resistant than bacteria to phenolic substances. The
fungal flora consists essentially of Aspergillus flavius, Aspergillus candidus, Pen-
icillium negricans, and Alternaria sp., while, no fecal bacteria was highlighted
(Mouncif et al. 1993b; Aissam 2003).
Thermal treatment, through evaporation in ponds (lagoons), represents the most
practiced treatment of OMW in Morocco (Fig. 7), although several methods have
been tested, but their application is limited. The options of valorization remain also
Fig. 7 Evaporation pond of

OMW (Taza province,
Morocco)
at laboratory scale. Hanafi et al. (2009) have the electrocoagulation method for
OMW treatment. A removal capacity of 80–85% COD, 75–80% phenolic
compounds, 96–99% color, 7–8 kg/m3 suspended solids, and a reduction of
more than 70% for orthophosphates, ammonium, zinc, and iron after 15 min of
electrolysis at 250 A/m2 were reported. Electrocoagulation was also tested as
pretreatment to enhance the fungal treatment. The electrocoagulation was able
to decrease the COD and phenol content of the 25% OMW by more than 80%
and the color by more than 90%. The strain Aspergillus niger van Tieghem was
more efficient to reduce COD, phenol content, and color when the OMW was
prior diluted or pretreated (Hanafi et al. 2010). Ben Sassi et al. (2010) have also
studied the biological process using yeast isolated from OMW. Result was a
reduction of about 50% of phenolic compounds. Achak et al. (2014) have used
the absorption onto wheat bran for the removal of phenolic compounds from
OMW in another study. The finding was a phenolic compounds adsorption rate
of 67% at 50 g/L of absorbent dose with an increase of adsorption capacity at
high alkanity.
Valorization options of OMW were also studied by several authors. El-Abbasi
et al. (2012) have revealed the considerable antioxidant capacity of the OMW,
which can be considered as an inexpensive potential source of high added value
powerful natural antioxidants comparable to some synthetic antioxidants com-
monly used in the food industry. El Yamani et al. (2017) also reported a high
antibacterial activity of phenolic compounds extracted from OMW. Belaqziz et al.
(2016) have investigated the effect of direct amendment of OMW on the fertility of
soil, described as poor in the area of Marrakech (semi-arid region) in Morocco.
Results of amendment with untreated OMW for two consecutive years (10 L/m2/
year) were increase of nutritive elements by 81% for nitrogen, 66% for phosphorus
and 88% for potassium in soil. The accumulation of phenolic compounds and the
increase of total peroxidase activity in plants have provided evidence of their
protective role against the physiological stress induced by OMW. Recently,
El-Abbassi et al. (2017) have reported that the OMW can be used to suppress the
growth of the main bacterial, fungal phytopathogens, and weed species without
any negative effects on crop growth. Nevertheless, some measures should be
respected when using OMW as biopesticide especially in regards of dose and
timing of use.
Conclusion
Technologically, the problem of OMW could be more or less solved after many
successful attempts at treatment and valorization. While realistically, it is still far
from being solved, mainly because of practical and economic reasons related to
nature of OMW, dispersion of the olive mills, and the seasonality of the process
(Paraskeva and Diamadopoulos 2006). Hence, the olive oil industry needs even
more studies on the development of olive oil extraction techniques or on the options
for removal of OMW toxicity and their valuation.
Cross-References
▶ Biofilm-based Systems for Industrial Wastewater Treatment

▶ Major Environmental Issues and Problems of South Asia, Particularly Bangladesh
▶ New Techniques for Treatment and Recovery of Valuable Products from Olive
Mill Wastewater
▶ Technologies for Treatment of Colored Wastewater from Different Industries
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Studies on Water Quality of Mokokchung
District, Nagaland, India, and Removal of 68
Trace Elements Using Activated Carbon
Prepared from Locally Available Bio-waste
Daniel Kibami
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1688
Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1690
pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1692
Electrical Conductivity (EC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1692
Total Dissolved Solids (TDS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1692
Total Alkalinity (TA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1692
Dissolved Oxygen (DO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1693
Total Hardness (TH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1693
Cations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1693
Anions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1693
Study of Trace Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1695
Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1695
Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1696
Manganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1697
Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1697
Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1697
Mercury (Hg) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1698
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1698
An Overview of Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1698
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1699
Preparation of Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1699
Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1701
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1712
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1713
D. Kibami (*)
Department of Chemistry, Kohima science college (Autonomous) Jotsoma, Kohima,
Nagaland, India

https://doi.org/10.1007/978-3-319-73645-7_92
1688 D. Kibami
Abstract
With an increasing level of pollution leading to quality deterioration, water
quality assessment and remediation is becoming one of the thrust areas of
research internationally. In acknowledgment of this, a preliminary investigation
was done under the topic “Studies on Water Quality of Mokokchung District,
Nagaland, India and Removal of Trace Elements Using Activated Carbon Pre-
pared from Locally Available Bio-Waste” which has now come to form the
subject matter of this project.
Two aspects of study were taken up which include physicochemical analysis
of water quality of Mokokchung district and also studies on the use of activated
carbon for removal of trace elements. Accordingly, the studies on the quality of
water of Mokokchung district have been presented as one full chapter. Again, the
work on synthesis of activation carbon using two different adsorbents has been
discussed. Studies of their application in removal of trace elements like Pb has
been done using batch adsorption technique which includes effects of various
experimental parameters such as initial concentration, contact time, and
pH. Adsorption data fitted well with all the adsorption isotherm models. How-
ever, Freundlich isotherm displayed a better fitting model; this indicates the
applicability of multilayer coverage of the Pb (II) on the surface of adsorbent.
The adsorption kinetics was studied using four simplified models, and it was
found to follow the pseudo-second-order kinetic model. The adsorption mecha-
nism was found to be chemisorption and the rate-limiting step was mainly surface
adsorption.
Keywords
Pollution · Water quality · Mokokchung district · Activated carbon · Batch
adsorption · Adsorption isotherm · Freundlich isotherm · Adsorption kinetics ·
Chemisorption
Introduction
The quality of drinking water is a powerful environmental determinant of health

(World Health Organization 2011). According to the World Health Organization,
drinking water must be free of chemicals and microbial contaminations which are
risk to human health. Good drinking water quality is essential for the wellbeing of all
people (World Health Organization 2011; APHA 1985). It has been reported that
increasing population and its necessities have led to the deterioration of surface and
subsurface water (USEPA 1979; Rao and Mamatha 2004). It is therefore vital to
regularly monitor the quality of water by studying the physicochemical properties of
water which are important not only in the assessment of the degree of pollution but
also in the choice of the best source and the treatment needed (World Health
Organization 1984).
68 Studies on Water Quality of Mokokchung District, Nagaland, India, and. . . 1689
In the state of Nagaland, the predominant sources of water are surface water from
rivers, streams, ponds, and natural springs and subsurface water occurring as ground
water. Information of water quality in Nagaland is very scanty, as there is very little
documentation on the state of rivers/water bodies, and thus monitoring is a very
recent phenomenon and so far has been taken up on a very limited basis (http://
npcbngl.nic.in/laboratory.htm). This study was considered important since
Mokokchung is a fast developing town of Nagaland, where rapid urbanization is
leading to rampant pollution of water sources, and hence, it was thought that a
preliminary study of surface and ground water quality would be of value for
developing management strategies for maintaining potable water quality.
Mokokchung with Latitude of 26.12 N and 26.45 N and a Longitude of
94.18 E and 94.50 E is situated in the north-eastern region of Nagaland state. It
is located 1325 meters above sea level and receives an annual rainfall of around
200 cm on an average (http://nagaland.nic.in). The present study was planned by
selecting (one sample from each colony/ward) different ground and surface water
sources around Mokokchung town (Fig. 1).
Fig. 1 Map of Mokokchung area

1690 D. Kibami
The water samples were collected from the various sources in separate container;
prewashed (with HNO3 and thoroughly rinsed with deionized water) sterilized
polyethylene bottles of 2 liters capacity were used for storing the water samples.
Parameters like water temperature, pH, electrical conductivity, total dissolved solid
(TDS), alkalinity, dissolved oxygen (DO) total hardness, calcium, magnesium chlo-
ride, sodium, potassium, phosphate, nitrate, and sulfate, fluoride were analyzed as
per standard procedures (World Health Organization 1984). Each sample was
analyzed in duplicate and the mean result reported. All The reagents used for the
analysis were AR grade, and double distilled water was used for preparation of
solutions (Table 1).
The physicochemical parameters of the water samples collected from 12 different

places.
In and around Mokokchung town is describing as below (Tables 2 and 3).
Temperature
Temperature is a significant factor which influences the abiotic and biotic com-
ponents of the environment. It helps in controlling the solubility of gases. The
Table 1 Determination of water quality parameters

Sl.No. Parameters Methods of determination
1. Temperature Thermometer
2. Hydrogen ion concentration (pH) pH metry
3. Electrical conductivity (EC) Conductometry
4. Total dissolved solids (TDS) Evaporation method
5. Alkalinity (ALK) as CaCO3 Titrimetry
6. Total hardness (TH)as CaCO3 EDTA -Titrimetry
7. Calcium (Ca) EDTA -Titrimetry
8. Magnesium (Mg) EDTA –Titrimetry
9. Sodium (Na) Flamephotometry
10. Potassium (K) Flamephotometry
11. Chloride (CI) (argentometric method) Titrimetry
12. Nitrate (NO3) Spectrophotometry
13. Sulfate (SO4) Spectrophotometry
14. Phosphate Spectrophotometry
15. Fluoride Fluoridemeter
16. Dissolved oxygen (DO) Titrimetry
Table 2 Results of physicochemical analysis of water

Electrical Total
Sl. Water Temperature conductivity TDS alkalinity
No. source Ward/colony
C pH μScm1 mg/L (TA)mg/L
1. Tap FAC campus 22.2 7.69 322 287 111.5
water
2. Stream Alisunkum 22.3 6.93 55.1 49.9 109
3. Bore Tondentsunyoung 22.6 6.50 332 297 106
well
4. Stream Alongmen 22.5 7.52 262 234 107.5
5. Pond Medical 22.4 7.01 204 185 112.5
6. Pond Majakong 22.6 6.55 214 180 111
7. Bore Salangtem 23.4 5.66 794 728 114.5
well
8. Pond Dilong 24.6 5.05 547 495 115.5
9. Bore Aongza 23.7 6.35 390 351 109.5
well
10. Stream Alempang 24.1 5.51 484 530 117.5
11. Pond Arkong 24.3 5.10 375 342 117
12. Bore Yimyu 22.3 7.16 215 189 113.5
well
Table 3 Indian standard specifications for drinking water IS: 10,500

IS:10500,1991
Sl. Requirement Permissible limit in absence of
No. Parameters (desirable limit) alternate source
1. Temperature ( C) – –
2. pH 6.5–8.5 No relaxation
3. EC (μScm1) 500 1000
4. TDS (mg/L) 500 2000
5. Total hardness as 300 600
CaCO3 (mg/L)
6. Total alkalinity (mg/L) 200 600
7. Calcium (mg/L) 75 200
8. Magnesium (mg/L) 30 100
9. DO (mg/L) 3 10
10. Chloride \(mg/L) 250 1000
11. Sulfate (mg/L) 200 400
12. Nitrate (mg/L) 45 100
13. Fluoride (mg/L) 1 1.5
temperature of the water samples analyzed did not have much variation and
was between 22.2 C and 24.6 C which indicated that the water samples were
in the natural state with less contamination from the effluents (Patil and Patil
2010).
1692 D. Kibami
pH
pH is an important factor which expresses the acidic or alkaline nature of a solution.

According to Fakayode, S.O. (Fakayode 2005), the pH of a water body is very
important in determination of water quality since it affects other chemical reactions
such as solubility and metal toxicity (Kataria 1995). The pH values vary from 5.10 to
7.62 where water samples collected from Salangtem, Dilong, Aongza, Alempang,
and Arkong (sample no.7, 8, 9, 10, and 11) were found below the prescribed limit.
This lower limit indicates the corrosive nature of the water samples collected which
is not fit for drinking purpose and its prolong use may cause serious health problems
(Golterman et al. 1978; Maiti 1982).
Electrical Conductivity (EC)
Conductivity is the ability of water to carry an electrical current. It is a rapid method

to measure the total dissolved ions and is directly related to the amount of total
dissolved salts (USEPA 1979). An observation of the results reveals the non-
uniformity in the variation of EC values in all samples. EC values in water samples
ranged from 55.1 to 794 μ mhos/cm. Most of the water samples collected lies in the
range of excellent and good category and can be used for both drinking as well for
irrigation purpose (John 1997; Anil Kumar De 1989).
Total Dissolved Solids (TDS)
Total dissolved solids indicate the nature of salinity in water (USEPA 1978). It also
gives an idea about suitability of the water for various uses. Dissolved solids tend to
increase with increasing pollution of water. TDS above 500 mg/L is not considered
desirable for drinking. The TDS values for study area have varied from 49.9 to
728 mg/L. Most of the water samples lie below the permissible limit. High TDS
values for Salangtem and Dilong (sample 7 & 10) could be due to presence of high
content of Ca2+, CI-.\, and Na+ ions in the water (Anil Kumar De 1989; Keller and
Pitblade 1986).
Total Alkalinity (TA)
Alkalinity of water is a measure of its capacity to neutralize strong acids and is due
to the presence of bicarbonate, carbonate, and hydroxide compound of calcium,
sodium, and potassium (Gilbert Masters 2013). The observed values of alkalinity
ranged between 106 and 117.5 mg/L in water. According to United States envi-
ronmental protection agency (USEPA 1979), the maximum permissible limit of
total alkalinity is 120 mg/L. Here the observed values are within the permissible
limit.
Dissolved Oxygen (DO)
Dissolved oxygen refers to the amount of oxygen dissolved in the bodies of water. It
is a relative measure of the amount of oxygen that is dissolved or carried in a given
medium. Insufficient oxygen often caused by the decomposition of organic matter
tends to suppress the presence of aerobic organism. The levels of dissolved oxygen
varied from 6.90 to 15.20 mg/L, which is within the desirable limit as Prescribed by
ISI (Indian Standard Institute 1993). The high value of DO for the water samples
may be due to wave action, pollution load, organic matter, and photosynthetic
activity (NEERI 1979; Suess 1982; Kannan et al. 1993).
Total Hardness (TH)
Total hardness is determined by the concentration of multivalent cations (usually

Mg2+ and Ca2+) in water (Somasekhara Rao and Someswara Rao 1995). It is usually
expressed as the equivalent of CaCO3 concentration. Hardness is commonly under-
stood as a property of water, which prevents the lather formation with soap. Total
hardness for the samples under study was found to vary between soft and moderately
soft category with their hardness values in the range of 55–150 mg/L (Table 4).
Cations
The cations analyzed in the present study includes calcium, magnesium, sodium, and
potassium. For the study area, the concentration of calcium has varied from 8.01 to
29.65 mg/L which is well below the permissible limit (IS 1050092 recommended its
desirable upper limit at 75 mg/L), whereas the concentration of magnesium varies
from 2.43 to 15.10 mg/L in the study area (upper limit IS10500-91 for Magnesium is
30 mg/L). For the study area, water is in the range of soft and moderately soft
category which is due to the low concentration of calcium and magnesium ions
present in the water. Potassium content in the water samples varied from 1.0 mg/L to
11.0 mg/L which is well below the recommended limit, whereas the concentration of
sodium ranges from 3.0 to 53.0 mg/L in the study area. Sodium in drinking water
normally presents no health risks, as about 99% of the daily salt intake is from food
and only about one percent from water (U.S. Environmental Protection Agency
1991; Kumar and Sinha 2010; WHO regional office for Europe 1979).
Anions
For the present study, the anions analyzed were chloride, sulfate, phosphate, nitrate,
and fluoride. The concentration of chloride in all the samples in the study area ranges
from 11.36 to 63.90 mg/L (permissible value for drinking water standard as per
IS10500-91 is 250 mg/L), which indicated low level of pollution by sewage disposals
1694
Table 4 Results of physicochemical analysis water samples

Dissolved oxygen (DO) Total hardness (TH) Ca Mg CI NO3 SO4 K Na F PO4
Sl.No. mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L
1. 7.00 125 15.23 2.92 14.21 0.194 7.83 11.00 8.00 1.76 0.75
2. 7.80 100 8.01 4.87 21.31 0.113 7.79 1.00 3.00 0.43 0.41
3. 9.00 145 29.65 15.10 42.63 0.010 14.01 1.00 10.00 1.24 0.30
4. 13.00 130 20.04 6.33 35.52 0.016 17.46 5.00 17.00 0.41 0.80
5. 6.90 55 18.43 5.84 32.66 0.080 16.60 3.00 20.00 0.57 0.70
6. 12.00 60 16.03 4.38 11.36 0.191 9.86 3.00 24.00 1.90 0.84
7. 12.50 85 26.45 5.36 63.90 0.005 12.76 3.00 53.00 0.15 0.42
8. 14.30 95 16.83 12.18 61.06 0.021 14.45 5.00 47.00 0.18 0.55
9. 15.20 125 17.86 9.49 14.20 0.028 16.54 2.00 22.00 1.35 0.40
10. 8.60 150 20.84 2.90 56.80 0.015 9.67 3.00 20.00 1.95 0.65
11. 14.50 70 8.21 6.81 51.12 0.141 8.47 2.00 39.00 0.19 0.59
12. 12.35 60 9.61 2.43 39.76 0.098 12.67 4.00 9.00 0.83 0.45
D. Kibami
(the concentration of chloride in water serves as an indicator of pollution by sewage

National Research Council 1972). Whereas the concentration of sulfate, phosphate, and
nitrate were found to be 7.79 to 17.46 mg/L, 0.30 mg/L to 0.84 mg/L, and 0.005 to
0.194 mg/L, respectively. These values were well below the permissible limits, and their
presence could only be from the natural sources (Bernard and Ayeni 2012; Delisle and
Schmidt 1977). The concentration of fluoride in all the samples in the study area has
varied from 0.15 to 1.95 mg/L. Fluoride content in FAC campus, Majakong, and
Alempang were beyond the permissible limits, which may be due to weathering of
minerals, rock dissolution where fluorine is leached out and dissolved in ground water
(Galagon and Lamson 1953; USEPA 1980; Katoky et al. 2008; Gupta et al. 1986, 1999,
2011; Haloi and Sharma 2011; Sarala Kumar and Rao 1993; Somani et al. 1972).
Study of Trace Elements
Trace elements, especially the so-called heavy metals, are a serious pollutant in our
natural environment due to their toxicity, persistence, and bioaccumulation problems
which is a threat to human life and the environment (Nassef et al. 2006). Trace
element pollution is one of the major problems coming with increasing of human
activities, especially near water resources and rivers (Fang and Hong 1999). Their
presence in the wastewater of several industrial processes, such as electroplating,
metal finishing, metallurgical work, tanning, chemical manufacturing, mining, and
battery manufacturing, has brought about more environmental concerns due to their
toxicity even at low concentrations. (Rajappa et al. 2010; Weaver et al. 1961; Fatoki
and Hill 1994). Many studies have focused on the determination of trace pollutants
particularly heavy metals like Cu, Zn, Pb, and Hg in different sites highly polluted by
domestic, agricultural, and industrial wastes worldwide (ATSDR 2000; Griffin 1960;
Trivedy and Goel 1986; The report of the scientific review committee Ottawa 1990).
The objectives of the present investigation were to find out the status of the trace
elements in water in the study area. For this study, the presence of different trace
element in the water was planned to be studied. The following trace elements, i.e.,
iron, zinc, lead, manganese, arsenic, and mercury, were chosen. They are classified
as highly toxic and moderately toxic or less toxic in nature. The results of the
analysis of trace elements in the study area are given in Table 5.
The significance of the presence of individual trace element is discussed below.
Iron
Iron is one of the most abundant metals in the earth’s crust. It is an essential element
in human nutrition. The common sources of iron in groundwater are weathering of
iron bearing minerals and rocks, industrial effluent, acid-mine drainage, sewage, and
landfill leachate. In drinking water, Fe (II) salts are unstable and are precipitated as
insoluble Fe (III) hydroxide, which settles out as a rust-colored silt.
Iron may also be present in drinking water as a result of the use of iron coagulants or
the corrosion of steel and cast iron pipes during water distribution. Iron also promotes
1696 D. Kibami
Table 5 Results of physicochemical analysis of water samples

Fe Pb Mn As Zn Hg
Sl.No. Ward/colony mg/L mg/L mg/L mg/L mg/L mg/L
1. FAC campus 3.200 3.00 0.00 0.00 0.00 0.00
2. Alisunkum 0.091 0.062 0.063 0.019 1.542 0.00
3. Tondentsunyoung 0.145 0.023 0.035 0.027 0.065 0.00
4. Alongmen 0.295 0.034 0.022 0.011 1.108 0.00
5. Medical 0.193 0.104 0.505 0.044 1.274 0.00
6. Majakong 0.154 0.101 0.176 0.014 0.921 0.00
7. Salangtem 0.098 0.001 4.801 0.000 0.00 0.00
8. Dilong 0.082 0.023 0.195 0.017 1.347 0.00
9. Aongza 0.156 0.024 0.486 0.046 1.234 0.00
10. Alempang 0.144 0.048 0.367 0.048 1.643 0.00
11. Arkong 0.246 0.035 0.474 0.014 1.972 0.00
12. Yimyu 0.275 0.029 0.234 0.045 0.450 0.00
undesirable bacterial growth (“iron bacteria”) within a waterworks and distribution

system, resulting in the deposition of a slimy coating on the piping (Weaver et al.
1961; Florence 1977). Iron in water can cause yellow, red, or brown stains on laundry,
dishes, and plumbing fixtures such as sinks. Normally it causes slight toxicity, but
excessive intake can cause siderosis and damage to organs through excessive iron
storage (Indian council of Medical Research 1975). It is observed that the concentration
of iron has varied from 0.091 to 3.200 mg/L in the study area. The water sample from
FAC campus (sample 1) showed a high Fe content, whereas the other water samples
collected in the area under study had Fe concentration below the desirable limit. One of
the reasons for high concentration of Fe lying in these water bodies might be due to the
presence of iron-rich soil layers and sediments. Another reason could be due to the
presence of wastes that get to the surface as effluent discharges (Rajappa et al. 2010).
Lead
Lead occurs naturally in the environment. However, most lead concentration that is
found in the environment is a result of human activities. The presence of lead is
primarily from household plumbing systems containing lead in pipes, solder, fittings,
or the service connections to homes. This is more likely to happen when the water is
slightly acidic. Other sources of lead include organo-lead compounds, which is used
extensively as antiknock and lubricating agents in petrol, although their use for these
purposes in many countries is being phased out (Fatoki and Hill 1994).
The World Health Organization has established 0.05 mg/L as a tentative limit for
lead in drinking water. The present study has showed that the concentration of lead
varied from 0.001 to 3.00 mg/L in water samples. The water samples collected from
all the area under study, except in FAC campus (sample 1), Medical (sample 5), and
Majakong (sample 6), generally have values below the permissible limit. The high
concentration of lead in this water samples could be due to extensive use of lead
piping in the household plumbing system (Scoullos et al. 2001).
Manganese
Manganese occurs naturally in many surface water and groundwater sources. In

surface waters, manganese occurs in both dissolved and suspended forms, depending
on factors like pH, anions present, and oxidation–reduction potential (Griffin 1960).
The manganese ion imparts an undesirable taste to beverages and stains plumbing
fixtures and laundry (Hanaa et al. 2000). The stains caused by manganese are harder
than those of iron to remove. The maximum permissible limit of manganese in water
is 0.5 mg/L. The careful observation of the results indicates that the distribution of
manganese concentration is not uniform in the study area. Some of the water samples
do not contain manganese, whereas in two samples (no.5 and 7) the concentration of
manganese was found to be well beyond the permissible limit.
Arsenic
Arsenic is a natural element which occurs in many environmental compartments

such as rock, soil, water, and air as well as in plant and animal tissues. Whatever it is
natural or industrial origin, it is often responsible for the contamination of water
supplies. Depending on the physicochemical condition of the environment, some
arsenic compounds can be highly soluble, resulting in a high level of bioavailability.
The presence of these compounds has therefore been declared as a major risk to
human health in various parts of the world. Drinking well water with low to
moderately elevated levels of arsenic over a long period of time may lead to chronic
health effects (Klavins et al. 2000; Hanaa et al. 2000).
Chronic health effects, such as cancer, develop over a number of years and can be
difficult to detect, especially in the early stages. Higher levels of arsenic can also lead
to more immediate or acute health effects that usually have more noticeable symp-
toms. For arsenic in drinking water, a provisional guideline value of 0.05 mg/l is
recommended (ISI-IS: 2296-1982). In the present study, the concentration of arsenic
varied from 0.00 to 0.048 mg/L which is within the permissible limit. The result
reveals that the distribution of arsenic concentration is not uniform in the study area.
Zinc
Zinc is an essential trace element found in virtually all food and potable water in the
form of salts or organic complexes. WHO has established 5 mg/L as the highest
desirable level and 15 mg/L as the maximum permissible limit for zinc in water for
domestic use. Zinc is required and is a beneficial element in human metabolism. A
deficiency of zinc in the diet of the children leads to growth retardation (Majumdar
2003). Zinc may be toxic to aquatic organisms, but the degree of toxicity varies
greatly depending on water quality characteristics as well as the species being
considered. In the present study, the concentration of zinc has been observed to be
varying from 0.00 to 1.97 mg/L in the study area. The results indicate that the
concentration of zinc is below the maximum permissible limit in all the samples.
1698 D. Kibami
Mercury (Hg)
Mercury occurrence is generally industrial in origin. It is used in the electrolytic

production of chlorine, in electrical appliances, in dental amalgams, and as a raw
material for various mercury compounds. It is a very toxic element, especially when
methylation of inorganic mercury occurs in fresh water and in seawater (Michael
Scoullos et al. 2001), although almost all mercury in uncontaminated drinking water
is thought to be in the form of Hg2+. Thus, it is unlikely that there is any direct risk
of the intake of organic mercury compounds. However, there is a possibility that
methyl mercury will be converted into inorganic mercury. Food is the main source of
mercury in nonoccupationally exposed populations; the mean dietary intake of
mercury in various countries ranges from 2 to 20 mg/day per person. In cases
of mercury poisoning of any type, the kidney is the organ with the highest
bioaccumulation of mercury. Mercury was not detected in any of the water samples
in the area understudy.
Conclusion
The analysis of the water quality parameters from different places around
Mokokchung town indicates that electrical conductivity, TDS, total alkalinity, total
hardness, calcium, magnesium, chloride, sodium, potassium, dissolved oxygen, and
sulfate are well within the permissible limits. However, some of the water samples
collected showed low pH value indicating the corrosive nature of this water samples,
which may be due to the presence of toxic metals such as Pb and Cu. Low degree of
effluents sources of nitrate and phosphate was observed as concentration of nitrate
and phosphate in water was minimal. Fluoride content in water samples collected
from FAC campus, Majakong, and Alempang was above the permissible limit. It
was found that the concentrations of some of the elements were found to be above
the permissible limits, whereas in some areas elements such as Zn, As, Hg, and Pb
could not be detected as it was below the detection limit. The study is done for one
set of samples. However, in order to understand the proper seasonal variation, a
detailed study for 3 years might be required. The results reported here are an initial
report of water quality of Mokokchung district (Kibami et al. 2013).
An Overview of Activated Carbon
This section contains a brief account of activated carbons. Considering that the
uniqueness of activated carbons is because of their role as adsorbents, this term as
well as the term porosity have also been briefly explained. This section also contains
a concise discussion on metal ions as water pollutants, with special emphasis on
trace elements which are found in water, such as manganese and lead. The method-
ology that has been developed in this study for removal of Pb, based on biosorption
has also been explained.
Introduction
The presence of lead in drinking water is hazardous to the environment and public
health because of its toxic effects (Bahadir et al. 2007). The chief sources of lead in
water are from the effluents of processing industries (Nadeem et al. 2005;
Bhattacharjee et al. 2003; Sekar et al. 2004; Rivail Da Silva et al. 1996). Lead
produces a variety of adverse effects on cellular function and primarily affects the
nervous system, gastrointestinal tract, and hematopoietic system (Tong 1998).
Chronic lead poisoning occurs when small amounts of lead are taken in over a
longer period (Volesky 1990). According to the US Environmental Protection
Agency (EPA), the permissible level for lead in drinking water is 0.05 mg L1
(Bhattacharjee et al. 2003) and that of Bureau of Indian Standards (BIS) is 0.1 mg/l
(BIS 1981). Therefore, a very low concentration of lead in water is very toxic
(Bhattacharjee et al. 2003). Removal of lead in water thus assumes a very important
part in the process of water treatment.
At present, various methods like chemical precipitation, electrochemical reduc-
tion, ion exchange, reverse osmosis, membrane separation, and adsorption have been
developed to remove Pb2+ from wastewater (Connell et al. 2008; Acharya et al.
2009; Ricordel et al. 2001; Saeed et al. 2005; Doyurum and Celik 2006). Adsorption
of activated carbon has been shown to be very effective for the removal of toxic
metal ions from aqueous solutions. However the high cost of activated carbon limits
its use especially in developing countries. This has led for the search of activated
carbons from cheap and renewable sources by various researchers over the years
(Ferro-Garcia et al. 1990; Sohail and Qadeer 1997; Netzer and Hughes 1984). In our
study, activated carbon prepared from common bamboo and common buckwheat
plant was used owing to its easy availability in the area. Moreover, it requires little
processing and was thus inexpensive.
Preparation of Activated Carbon
Preparation of Activated Carbon by Indigenous Method

For this study, the initial carbonization is done at bamboo mission Dimapur, Naga-
land, India. In the bamboo mission, indigenous method of preparation of bamboo
charcoal (taken from Bamusa vulgaris/BVC) is done for commercial purpose. In this
process, the whole bamboo culms are cut into a uniform size of 1 m each so that it fits
into the kiln and stacking is easier. The bamboo is placed through the door at the
bottom and is stacked horizontally in the kiln (Fig. 2). The door is then closed with
bricks and plastered with mud on the outside for better insulation and to prevent
leakage. The feed is fired through the opening at the top of the kiln, and once the feed
is ignited, the opening is closed. During the initial stages of firing, the openings in
the wall of the kiln are kept open to create the required draft. Initially black smoke
will be emitted from the opening at upper end after which it will change to dense
1700 D. Kibami
Fig. 2 Bamboo charcoal kiln

at bamboo mission Dimapur
white fumes. Once the black smoke changes, openings are closed one by one starting
from the top to bottom. Carbonization is achieved by maintaining the temperature at
400–500 C by regulating the openings both in horizontal and vertical directions. All
the openings are closed after 2 days so that air is not allowed to enter the kiln to prevent
the charcoal from catching fire. Cooling is done for a day to reduce the temperature to
100 C. The biomass is removed from the opening at the bottom of the kiln and is
washed, dried, and crushed and further subjected to chemical activation with 0.1 N
HNO3 and 0.1 N H3PO4, and for which the carbons were washed with double-distilled
water to remove the excess acid and dried at 150 C for 12 hours. All the activated
carbons are chemically activated with 0.1 N solution HNO3 and 0.1 N H3PO4. The
powdered activated carbon obtained after HNO3 and H3PO4 treatment has a particle
size in the range of 40–50 μm mesh. Another form of activated carbon in powder form
is prepared by the pyrolysis of Fagopyrum esculentum Moench (FEMC) (common
Buckwheat). The biomass were collected, washed, dried, and crushed before carbon-
izing in a Muffle furnace electrically heated at 600 C for 4 hours. The activated
carbon prepared was cooled to room temperature and washed with deionized water
until the effluent was clear in color. Finally the synthesized carbon was dried in oven at
110 C for 12 hour. The synthesized carbon is chemically activated with 0.1 N solution
HNO3 and H3PO4, respectively, under similar conditions to modify the chemical
structure. The surface modification of carbons was also done by subjecting to liquid
phase oxidation (Somasekhara Rao 1993).
Preparation of Lead (II) Solution

Stock solution of Pb(II) was prepared (1000 mg/l) by dissolving required amount of
Pb(NO3)2 in acidified double distilled water. The stock solution was diluted with
distilled water to obtain desired concentration ranging from 5 to 45 mg/l. All the
chemicals used were of analytical reagent grade. The lead (II) ions is analyzed by
atomic absorption spectroscopy at 283.3 nm, using graphite furnace Analytikjena
Vario-6. The calibration is carried out versus an aqueous standards curve.
Adsorption Studies of Lead on Activated Carbons by Batch Method

In order to understand the adsorption behavior of lead, various experimental param-
eters have been investigated using batch adsorption experiments. The effect of initial
concentration is studied by varying lead concentrations between 5 and 45 mg/L. The
effect of contact time was studied by varying the agitating time (range: 2–240 min) at
fixed optimum initial concentration of lead (20 mg/L) with optimum dose of
adsorbents (0.25 g/L), and also the effect of pH was studied ranging from 2 to 5.5.
The percentage removal of the lead and the amount of lead adsorbed were calculated
by the following equations.
ðCi Cf Þ
Percentage removal ¼ 100
Ci:

Ci Cf V
Amount adsorbed ðqeÞ ¼
M
where Ci and Cf are the initial and final equilibrium solution concentrations of the
lead (mg/L), V is the volume of the solution (L), and M is the mass of the activated
carbon (g). The data obtained have been analyzed for adsorption isotherms models
and intraparticle diffusion model.
Effect of Initial Concentration

The effect of initial concentration on the adsorption of lead was studied by varying
the initial lead concentration between 5 and 45 mg/L in 100 ml of lead solution and
adding 1 g of adsorbent with a contact time of 120 minutes. Effect of initial varying
concentration of Pb (II) ions showed that the percentage adsorption decreases with
increase in initial concentration of the adsorbate. This decrease in Pb (II) ions
uptake capacity with increase in initial metal concentration may be due to the
formation of clusters of carbon particles resulting in decreased surface area
(Montanher et al. 2005; Chen and Wu 2004). The variation of percent removal
of lead with increasing initial concentration and variation of the amount of lead
adsorbed with increasing initial concentration are shown in Figs. 3 and 4. The data
reveal that under identical experimental conditions, the order of adsorption capac-
ity of the various adsorbents is as BVC (HNO3) > BVC (H3PO4) > FEMC
(HNO3) > FEMC (H3PO4).
Adsorption Isotherm
The relationship between the amount of a substance adsorbed per unit mass of
adsorbent at constant temperature and its concentration in the equilibrium solution
is called the adsorption isotherm (Feng et al. 2004). Various adsorption isotherm
models are employed in this study to describe the experimental adsorption isotherm
(Langmuir 1918; Freundlich and Helle 1939; Temkin and Pyzhev 1940).
1702 D. Kibami
Fig. 3 Variation of percent BVC(HNO3)

removal of lead with 100 BVC(H3PO4)
increasing Initial FEMC (HNO3)
concentration FEMC(H3PO4)
99
98
% Removal
97
96
95
94
0 10 20 30 40 50
Initial Conc. (mg/L)
Fig. 4 Variation of the 5 BVC(HNO3)

amount of lead adsorbed with BVC(H3PO4)
increasing initial FEMC(HNO3)
concentration 4 FEMC(H3PO4)
3
qe (mg/g)
0
0 10 20 30 40 50
Ci (mg/L)
(a) Langmuir adsorption model:
The Langmuir adsorption model is the most common model used to quantify the
amount of adsorbate adsorbed on an adsorbent as a function of partial pressure or
concentration at a given temperature. It suggests the formation of monolayer adsorp-
tion and also the surface is energetically homogeneous (Feng et al. 2004). The
Langmuir equation that is valid for monolayer adsorption onto a surface is given
below
K L Ce
qe¼
1 þ aL Ce
The linear form of the Langmuir equation can be represented by
Ce aL 1
¼ Ce þ
qe K L KL
where Ce is the equilibrium metal ion concentration (mg/l), qe the amount of lead
adsorbed at equilibrium (mg/g), and aL/KL (mg/g) and 1/KL (L/mg) are Langmuir
constants related to adsorption capacity and energy of adsorption, respectively.
When Ce/qe was plotted against Ce, a straight line with a slope of aL/KL was obtained
as shown in Fig. 5. The R2 value of 0.8799–0.9962 is shown in Table 6. This showed
that the models have good correlation coefficient in all the cases. The essential
characteristics of the Langmuir equation can be expressed in terms of a dimension-
less constant called separation factor (RL, also called equilibrium parameter) which
is defined by the following equation (Özacar and Sengil 2004; Mall et al. 2006; Crini
et al. 2007)
0.20
0.18 0.40
0.16 0.35
0.14
Ce/qe (g/L)
Ce/qe (g/L)
0.30
0.12
BVC(HNO3) 0.25
0.10
FEMC(HNO3)
0.08 0.20
0.06
0.15
0.04
0.0 0.2 0.4 0.6 0.8 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
Ce (mg/L) Ce (mg/L)
0.24
0.65
0.22
0.60
0.20
0.55
0.18 0.50
Ce/qe (g/L)
Ce/qe (g/L)
0.16 0.45
BVC(H3PO4) FEMC(H3PO4)
0.14 0.40
0.35
0.12
0.30
0.10
0.25
0.08 0.20
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Ce (mg/L) Ce (mg/L)
Fig. 5 Langmuir adsorption isotherms for the removal lead by different adsorbents
1704 D. Kibami
Table 6 Comparison of Freundlich, Langmuir, and Temkin adsorption isotherm models

Frendulich isotherm R2 Log K 1/n qe(expt.) qe(cal) χ2
(mg/g) (mg/g)
BVC (HNO3) 0.9991 0.5453 0.3166 1.9840 1.9647 0.0001877
BVC (H3PO4) 0.9913 0.4380 0.3427 1.9628 1.9542 0.0000376
FEMC(HNO3) 0.9932 0.4868 0.5213 0.9823 0.9235 0.0035195
FEMC(H3PO4) 0.9984 0.3619 0.6589 0.9753 0.9155 0.0036664
Langmuir isotherm R2 Qmax b qe(expt.) qe(cal) χ2
(mg/g) (mg/g)
BVC (HNO3) 0.9781 0.1408 0.0588 1.9840 1.9659 0.0001651
BVC (H3PO4) 0.9962 0.3019 0.0795 1.9628 1.9392 0.0002837
FEMC(HNO3) 0.9333 0.5649 0.0943 0.9823 0.9102 0.0052923
FEMC(H3PO4) 0.8791 0.5771 0.1306 0.9753 0.9040 0.0052122
Temkin isotherm R2 BT AT qe(expt.) qe(cal) χ2
(L/g) (mg/ g) (mg/ g)
BVC (HNO3) 0.9629 0.3529 1.2776 1.9840 1.9245 0.0017844
BVC (H3PO4) 0.9844 0.4312 1.8338 1.9628 1.9142 0.0026411
FEMC(HNO3) 0.9342 0.3245 1.4681 0.9823 0.9056 0.0059281
FEMC(H3PO4) 0.9451 0.3538 1.3905 0.9753 0.8956 0.0065125
1
RL ¼
1 þ a L Ci
where Ci (mg L1) is the initial adsorbate concentration and aL (L mg-1) is the
Langmuir constant related to the energy of adsorption. The value of RL indicates
the shape of the isotherms to be either unfavorable (RL > 1), linear (RL = 1),
favorable (0 < RL < 1), or irreversible (RL = 0); the results from Table 2 show
RL < 1 in all the cases; this indicates a favorable isotherm for the adsorbents used
in this study.
(b) Freundlich Adsorption Model:
Freundlich isotherm is an empirical equation describing the heterogeneous

adsorption and assumes that different sites with several adsorption energies are
involved (Sekar et al. 2004; Crini et al. 2007). The linear form of the Freundlich
equation is shown below.
1
log qe ¼ log k þ log Ce
n
where Ce is the equilibrium metal ion concentration (mg/L), qe the amount of lead
adsorbed at equilibrium (mg/g), K and 1/n are the Freundlich constants incorporating
all the factors effecting adsorption capacity, an indication of favorability of metal
adsorption onto adsorbent (Freundlich and Helle 1939). The slope 1/n gives adsorp-
tion capacity and intercept log K gives adsorption intensity from the straight portion
of the linear plot obtained by plotting log qe versus log Ce which gives a straight line
with slope of 1/n with value of 0.3166–0.3658 (Fig. 6); Freundlich constants KF and
n were also calculated and are listed in Table 6.
(c) Temkin Isotherm Model:
The Temkin isotherm assumes that the heat of adsorption of all the molecules in a
layer decreases linearly due to adsorbent-adsorbate interactions and that adsorption
is characterized by a uniform distribution of binding energies, up to some maximum
binding energy (Areco and Afonso Areco and Afonso 2010). The isotherm assumes
that the fall in the heat of adsorption is linear rather than logarithmic as stated in
Freundlich expression (Teles de Vasconcelos and Gonzalez Beca 1993). Unlike the
Langmuir and Freundlich equation, the Temkin isotherm takes into account the
interactions between adsorbents and metal ions to be adsorbed and is based on the
assumption that the free energy of sorption is a function of the surface coverage
(Deng and Ting 2005). The Temkin isotherm is applied in the following form
RT
qe ¼ ln ðAT :Ce Þ
bT
0.8 0.8
0.6 0.6
0.4 0.4
Log qe (mg/L)
Log qe (mg/L)
0.2 0.2
BVC (HNO3) BVC(H3PO4)
0.0 0.0
-0.2 -0.2
-0.4 -0.4
-1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2
Log Ce (mg/L) Log Ce (mg/L)
0.8 0.8
0.6 0.6
0.4 0.4
Log qe (mg/L)
Log qe (mg/L)
0.2 0.2
0.0 FEMC (HNO3) 0.0 FEMC(H3PO4)
-0.2 -0.2
-0.4 -0.4
-1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
Log Ce(mg/L) Log Ce (mg/L)
Fig. 6 Freundlich adsorption isotherms for the removal of lead by different adsorbents
1706 D. Kibami
The linear form of Temkin equation is
RT RT
qe ¼ ln AT þ ln Ce
bT bT
qe ¼ β lnα þ β ln Ce
where β¼ bRTT
; α = AT, T is the absolute temperature in Kelvin, R is the universal gas
constant, 8.314 J/mol K, bT is the Temkin constant related to heat of sorption (J/mg),
and AT the equilibrium binding constant corresponding to the maximum binding
energy (L/g). The Temkin constants AT and bT together with R2 values are shown in
Table 6. A plot of qe vs. ln Ce yielded a linear line as shown in Fig. 7.
(d) Validity of Adsorption Isotherm Models
Chi-Square Analysis
To identify the suitable isotherm for sorption of lead (II) ions onto carbon adsorbents,
the chi-square analysis was carried out. The mathematical statement for chi-square
analysis is
5 5
4 4
3 3
qe (mg/L)
qe (mg/L)
2 2 BVC (H3PO4)
BVC (HNO3)
1 1
0 0
-1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2
ln Ce (mg/L) ln Ce (mg/L)
4.5 4.5
4.0 4.0
3.5 3.5
3.0 3.0
qe (mg/L)
qe (mg/L)
2.5 2.5
2.0 2.0
1.5 FEMC (H3PO4)
1.5 FEMC (HNO3)
1.0 1.0
0.5 0.5
0.0 0.0
-1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
ln Ce (mg/L) ln Ce (mg/L)
Fig. 7 Temkin adsorption isotherms for the removal of lead by different adsorbents
2
X qeðexpt:Þqeðcal:Þ
χ2 ¼
qeðexpt:Þ
where qe(expt.) and qe(cal.) are the experimental sorption capacity of lead (II) ions
(mg g-1) at equilibrium time and the corresponding value that is obtained from the
sorption model. If data from the model are similar to the experimental data, χ2 will
be a small number, while if they differ; χ 2 will be a bigger number (Meeenakshi and
Viswanathan 2007). χ2 values are low for Freundlich isotherm when compared to
other isotherms for all the four sorbents. This is also in accordance with their
corresponding R2 values.
Effect of Contact Time

The effect of contact time on the removal of lead was studied by varying the
agitating time (range: 2–240 minutes) at fixed optimum initial concentration of
100 ml lead (20 mg/L) with a dose of adsorbents (1 g/L). Removal efficiency and
adsorption capacity of the adsorbents increase sharply in the initial stage and then
gradually remain steady with the increase of agitation time (Fig. 8). The initial
fast adsorption may be attributed to large uncovered surface area of adsorbents.
With further increase in the agitation time, the availability of the uncovered
surface area gradually diminishes. The uptake was slower at the final phase due
to the internal surface adsorption attaining plateau region at equilibrium (Aroua
et al. 2008; Lo et al. Lo et al. 1999). The equilibrium was attained after shaking
for 120 min. After equilibrium was attained, the percentage of sorption did not
change with further increase in time. The decrease in the extent of removal of lead
after 120 min of contact time in some cases may be due to the desorption process
(Itodo et al. 2009).
Fig. 8 Effect of Contact time 100

on percent removal of lead
99
98
97
% Removal
96
95
BVC (HNO3)
BVC (H3PO4)
94
FEMC(HNO3)
FEMC(H3PO4)
93
92
0 50 100 150 200 250
Time (min)
1708 D. Kibami
Adsorption Kinetics
One of the most important factors in designing an adsorption system is predicting the
rate at which adsorption takes place, referred as the “‘kinetics of sorption.” Four
simplified kinetic models were adopted to examine the mechanism of the adsorption
process.
(a) Pseudo-First-Order Model:
Langergren and Svenska used rate equation to describe the adsorption of adsor-
bate from the liquid phase (Langergren and Svenska 1898); the linear form of
pseudo-first-order rate expression is given as
k1
logðqe qt Þ ¼ logqe t
2:303
where qe and qt (mg g1) are the adsorption capacities of lead(II) ions at equilibrium
and at time t (min), respectively, and k1 is the rate constant of pseudo-first-order
kinetics. The correlation coefficient (R55) and pseudo-first-order constant (k1) for
both adsorbents are summarized in Table 7. The values of R2 vary between 0.9682
Table 7 Comparison of kinetic models showing calculated qe(cal.) and experimental qe(expt.)
values
Pseudo-first-order reaction
Adsorbent qe (expt.)(mg g1) k1 qe(Cal.)(mg g1) SSE R2
101
BVC(HNO3) 1.9840 0.3721 1.9602 0.0001445 0.9850
BVC(H3PO4) 1.9628 0.3573 1.9222 0.0004279 0.9682
FEMC(HNO3) 1.9452 0.2570 1.8290 0.0035685 0.9898
FEMC(H3PO4) 1.9322 0.1967 1.6484 0.0215741 0.9858
Pseudo-second-order reaction
Adsorbent qe (expt.)(mg g1) K2 qe(Cal.)(mg g1) SSE R2
1
10
BVC(HNO3) 1.9840 3.5404 1.9711 0.0000425 0.9999
BVC(H3PO4) 1.9628 5.0845 1.9514 0.0000337 0.9995
FEMC(HNO3) 1.9452 2.3164 1.9373 0.0000165 0.9994
FEMC(H3PO4) 1.9322 2.8778 1.9258 0.0000109 0.9991
Intraparticle diffusion
Adsorbent qe (expt.)(mg g1) Kip qe(Cal.)(mg g1) SSE R2
1
10
BVC(HNO3) 1.9840 0.5730 1.9069 0.0015163 0.8767
BVC(H3PO4) 1.9628 0.7310 1.8670 0.0023823 0.9666
FEMC(HNO3) 1.9452 0.4840 1.8850 0.0009578 0.8317
FEMC(H3PO4) 1.9322 0.5440 1.8628 0.0012901 0.8429
and 0.9898, and the experimental qe values did not agree with the calculated values
obtained from the linear plots (Fig. 9).
(b) Pseudo-Second-Order Model:
The pseudo-second-order rate expression, which has been applied for analyzing
chemisorptions kinetics from liquid solutions (Ho 2004; Shrihari et al. 2005), is
linearly expressed as:
t 1 1
¼ 2
þ t
qt k2 qe qe
where k2 is the rate constant for pseudo-second-order adsorption (g mg1 min1)

and k2qe55 (mg g1 min1) is the initial adsorption rate. The linear plot of t/qt versus
t, as shown in Fig. 10, yielded R2 values that were greater than 0.999 for all
adsorbents. It also showed a good agreement between the experimental and the
calculated qe values (Table 7). Hence, it can be concluded that the adsorption for
both adsorbents was predominated by pseudo-second-order kinetic model.
(c) Intraparticle Diffusion Model:
-1.6 -1.4
-1.8 -1.6
BVC(HNO3)
-1.8
-2.0 -2.0 BVC(H3PO4)
Log (qe-qt)
Log (qe-qt)
-2.2
-2.2
-2.4
-2.4 -2.6
-2.8
-2.6
-3.0
-2.8 -3.2
0 10 20 30 40 50 60 0 10 20 30 40 50 60
time (t) mins time (t) mins
-1.2
-1.2
-1.4
-1.4
FEMC(HNO3) -1.6
-1.6
FEMC(H3PO4)
Log (qe-qt)
-1.8
Log (qe-qt)
-1.8 -2.0
-2.2
-2.0 -2.4
-2.6
-2.2 -2.8
-3.0
-2.4
0 20 40 60 80 0 20 40 60 80
time (t) mins time (t) mins
Fig. 9 Pseudo-first-order kinetic model fit for Pb(II) Ions adsorption on the adsorbents
1710 D. Kibami
Fig. 10 Pseudo-second-order 70
kinetic model fit for Pb
(II) Ions adsorption on the 60
adsorbents
50
40
t/qt
30
BVC(HNO3)
20 BVC(H3PO4)
FEMC(HNO3)
10 FEMC(H3PO4)
0 20 40 60 80 100 120
Time (t) mins
Intraparticle diffusion is a transport process involving the movement of spe-

cies from the bulk of the solution to the solid phase. In a well-stirred batch
adsorption system, the intraparticle diffusion model has been used to describe
the adsorption process occurring on a porous adsorbent (Weber and Morris 1962;
Özacar and Sengil 2005). According to Weber and Morris (1962), if the rate
limiting step is intraparticle diffusion, a plot of solute adsorbed against the square
root of the contact time should yield a straight line passing through the origin
(Gerente et al. 2007). Also the rate constant for intraparticle diffusion is obtained
from the slope of the curve. Weber and Morris (1962) theorized that the rate of
intraparticle diffusion varies proportionally with the half power of time and is
expressed as:

qt ¼ Kid t1=2 þ C
where qt = adsorbate uptake at time t, (mg/g) and Kid = the rate constant of
intraparticle transport, (mg/g-t 1/2), which can be evaluated from the slope of the
linear plot of qt versus t 1/2. The values of intercept, c, are related to the boundary
layer thickness, i.e., the larger the value of the intercept, the greater is the boundary
layer effect (Shrihari et al. 2005; Weber and Morris 1962). Figure 11 shows the
multilinearity in intraparticle diffusion plots for Pb(II) adsorption with different
adsorbents. This indicates that intraparticle diffusion was not the only involved for
Pb(II) adsorption, but there were some other processes involve in the rate controlling
step. This suggests that adsorption occurred in three phases: the initial steeper
section represents surface or film diffusion, the second linear section represents a
gradual adsorption stage where intraparticle diffusion is rate-limiting, and the third
section is final equilibrium stage. Thus, there were three processes controlling the
adsorption rate.
2.00
1.98
1.96
1.94
qt (mg/g)
1.92
1.90
BVC (HNO3)
BVC (H3PO4)
1.88
FEMC(HNO3)
FEMC(H3PO4)
1.86
1.84
0 2 4 6 8 10 12 14 16
t (1/2) min
Fig. 11 Intraparticle diffusion plots for the removal of lead by adsorption on various adsorbents
(d) Validity of the Kinetic Models:
The best-fit among the kinetic models was assessed by the squared sum of errors
(SSE) values. It is assumed that the model that gives the lowest SSE values is the best
model for the particular system (Adhikary et al. 1989; Ho et al. 2000; John Freund
1981). The SSE values were calculated by the equation.
2
X qeðexpt:Þqeðcal:Þ
SSE ¼
qe 2 ðexpt:Þ
where qe(expt.) and qe(cal.) are the experimental sorption capacity of Lead (II) ions
(mg g-1) at equilibrium time and the corresponding value that is obtained from the
kinetic models. SSE values are least for pseudo-second-order kinetic model when
compared to other models; this is also in accordance with their corresponding R2
values which suggest kinetic adsorption follows pseudo-second order.
Effect of pH
pH is one of the key parameters which controls the adsorption efficiency by
influencing the surface charges (Kannan and Rengasamy 2005). It is an important
environmental factor influencing not only site dissociation, but also the solution
chemistry of the heavy metals: hydrolysis, complexation by organic and inorganic
ligands, redox reactions, and precipitation. It strongly influences the speciation and
adsorption availability of heavy metals (Esposito et al. 2002). The effects of initial
1712 D. Kibami
99
98
97
96
% Removal
95
94
93 BVC (HNO3)
BVC (H3PO4)
92 FEMC (HNO3)
FEMC(H3PO4)
91
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
pH
Fig. 12 Effect of pH on percent removal of Lead
pH on lead solution were investigated by varying the pH from 2 to 5.5 and using
initial lead concentration of 20 mg/L in 100 ml of lead solution with 1 g of adsorbent.
The lead adsorption usually increases as the pH is increased attaining optimum
capacity at pH: 5.5 (Shukla et al. 2002; Jalali et al. 2002). Above pH 5.5, Pb(II) starts
precipitating as Pb(OH)2 and hence studies above this range are not conducted
(Patnukao et al. 2008) (Fig. 12).
Conclusions
Adsorption studies of lead on activated carbons was studied by batch method where
effect of initial concentration and pH were the parameters considered for determin-
ing the adsorption efficiency of the carbon samples. The results of the percentage
removal of lead increased with the increase of contact time and pH. On the contrary,
the percentage of removal decreased with the increase in initial concentration of the
standard lead solution. The equilibrium data were analyzed using Langmuir,
Frendulich and Temkin adsorption isotherms. Frendulich isotherm displayed a better
fitting model than the other two models with a higher correlation coefficient of
0.99915 to 0.99138 indicating a multilayer adsorption. Three adsorption kinetic
models were studied; the pseudo-second-order kinetic model accurately described
the adsorption kinetics. The results show intraparticle diffusion was not the only rate
limiting factor in adsorption of Pb(II) ions. The adsorption mechanism was found to
be chemisorption and the rate-limiting step was mainly surface adsorption. Results
from this study suggest that the both the adsorbents under study are very effective
adsorbent for Lead (II) ions, as anticipated.
Cross-References
▶ Assessment of Some Aspects of Provisioning Sewerage Systems: A Case Study of

Urban Agglomerations in Ganga River Basin
▶ Water Quality Assessment of an Unexplored Tropical Freshwater System in
Thiruvananthapuram, India: A Multivariate Statistical Approach
Acknowledgments The authors acknowledge the staff of SAIF, NEHU Shillong for providing
necessary laboratory facilities for analyzing lead samples.
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Advancement of Photocatalytic Water
Treatment Technology for Environmental 69
Control
Sze-Mun Lam, Jin-Chung Sin, and Abdul Rahman Mohamed
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1720
Advancements in Photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1722
Synthesis of Various Bismuth Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1722
Photocatalyst Modification and Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1729
Supported Photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1731
Multivariate Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1732
Energy Consumption and Economic Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1733
Electrical Energy Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1733
Total Operating Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1734
Photocatalytic Disinfection in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1736
Water Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1736
Turbidity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1736
Oil and Grease . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1737
Trace Contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1738
Conclusion and Future Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1740
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1741
S.-M. Lam (*)

Department of Environmental Engineering, Faculty of Engineering and Green Technology,
e-mail: lamsm@utar.edu.my
J.-C. Sin
Department of Petrochemical Engineering, Faculty of Engineering and Green Technology,
A. R. Mohamed
School of Chemical Engineering, Universiti Sains Malayisia, Engineering Campus, Nibong Tebal,
Pulau Pinang, Malaysia

https://doi.org/10.1007/978-3-319-73645-7_93
1720 S.-M. Lam et al.
Abstract
Semiconductor photocatalytic process has been garnered a great interest in the
topic of green technology as it aims at the total elimination or at least the
minimization of waste production and the sustainable processes implementation
in the water or wastewater industry. The viable of this green technology has been
extensively shown to destruct a myriad of toxic organic pollutants and microbes
in water. This chapter reviews the recent advancement of engineered-
photocatalysts, modification strategy of photocatalysts, process optimization, as
well as energy consumption and economy analysis on the photodegradation
processes for water treatment. A number of potential photocatalysts are
discussed, in particular the bismuth-based photocatalysts. This chapter also
describes the utilization of multivariable approach to evaluate the optimum
parameters synthesis and process variables so as to enhance the photodegradation
efficiencies. The energy consumption and economy analysis that elucidated the
light utilization efficiency in the photocatalytic water treatment are presented. A
brief discussion on the photocatalytic disinfection of microbes in the water
treatment as an alternative waste treatment process is outlined. The water quality
that significantly influenced on the photodegradation performances is also
detailed. This present chapter will provide a useful scientific and technical
information to researchers and engineers who partake in this area.
Keywords
Organic pollutant · Semiconductor · Photocatalysis · Solar · Environmental
control
Introduction
Environmental pollution as well as the lack of natural energy resources has

garnered significant interest to the crucial need for chemical technologies and
ecologically clean materials. Photocatalysis is one of the most promising solutions
not only to circumvent the environmental pollutions but also as an efficient route to
harness solar energy as an alternative natural sources due to the depletion of
conventional energy sources. This process is also technically defined as an increase
in the rate of a thermodynamically allowed (ΔG < 0) reaction in the presence of
photocatalysts with the increase originating from the creation of some new reaction
pathways containing photogenerated species and a reduction of the activation
energy (Lam et al. 2012). The catalysts in photocatalytic reactions are normally
semiconductor materials, which have a band gap that separated the top of the
electron-filled valence band from the vacant conduction band. Upon irradiation of
semiconductor materials with light energy equivalent to or greater than their band
gap energies (Eg), the electron (e) excited from the valence band to the conduction
band, thereby creating an e and a hole (h+) in the conduction band and valence
69 Advancement of Photocatalytic Water Treatment Technology for. . . 1721
band, respectively. A band model is often used for schematic illustration of the
electronic structures of semiconducting materials (Fig. 1). Both the photogenerated
e and h+ diffused to the surface of semiconductors to undergo reactions either
oxidation or reduction with the absorbed compounds. The combination of e with
oxygen formed superoxide anion (O2•–) radicals, followed by reacting with H+
(producing hydroperoxyl (HO2•) radicals) and then further decomposition to form
hydroxyl (•OH) radicals. The •OH radicals are powerful oxidants to degrade the
organic pollutants in the photocatalytic system. At the same time, the adsorbed
water molecules on the surface of semiconductors are oxidized by h+ in the valence
band to form •OH radicals. It was also noted that the photogenerated e can easily
recombine with h+ after their generation in the absence of e or h+ scavengers. In
this regard, the presence of species scavengers is crucial for inhibiting the charge
carrier recombination and for enhancing the efficiency of photocatalytic reaction
(Paola et al. 2012; Dong et al. 2015).
To date, the most extensively used photocatalyst in the research of water and
wastewater treatment is Degussa P25 TiO2 catalyst. This catalyst is typically utilized
as a standard reference for comparisons of UV photoactivity under different treat-
ment conditions. On the contrary, exploration of a visible light active photocatalyst is
highly warranted and the light absorption of suitable energy is determined by the
band gap of the semiconductors. Among the semiconductors, bismuth photocatalysts
is a new type of promising visible light-responsive photocatalyst for the organic
pollutants. Degradation owing to its appropriate band gap and excellent chemical
stability (Sivakumar et al. 2014; Meng and Zhang 2017; Lam et al. 2017). Their
photoactivities can be enhanced by size and morphological changes on the catalytic
surfaces which lead to the reduction of the recombination of e–h+ pairs. On the
contrary, doping metal oxides have a positive impact on the photocatalytic effect,
which can be attained by allowing charge carrier transportation between the photo-
catalyst, and coupling with an additional phase could delay the recombination of
charge carriers. Therefore, the preparation and utilization of bismuth photocatalysts
have attracted a great interest (Tseng and Lin 2014; Henriquez et al. 2017; Wang
et al. 2017; Wu et al. 2017).
Fig. 1 Schematic of the

mechanism of photocatalytic
conversion of organic
pollutants
Different bismuth phosphate (BiPO4) nanostructures such as particle-like, rod-

like, needle-like, and rice-like were selectively synthesized to study the effect of
BiPO4 morphologies on the degradation of methyl orange (MO). The highest
activity of BiPO4 nanoparticles could be ascribed to its intrinsic distortion of PO4
tetrahedron and the smaller band gap structure (Li et al. 2011). Various bismuth
oxyhalides BiOXs (X = Cl, Br, I) (Wang et al. 2015) and bismuth ferrite oxides
(BiFeO3) (Gao et al. 2016) were also found to be capable of photo-destruction of
either in visible light or non-absorbing visible light water pollutants. This review has
surmounted the synthesis methods of bismuth compounds related to morphologies
and their modified strategies for photocatalytic efficiencies over various toxic and
persistence organic pollutants. The future challenges and opportunities on the way to
implement photocatalytic materials have been outlined to assist on the development
of energy research and finding ways to approach for the major problems.
Advancements in Photocatalysts
Synthesis of Various Bismuth Compounds
Synthesis of BiOX (X = F, Cl, Br, I)

Bismuth oxyhalides BiOX (X = F, Cl, Br, I) are bismuth-based semiconductors that
have demonstrated promising applications in pigments, pharmaceuticals, catalysts,
and gas sensors as a result of their outstanding optical and electrical proper-
ties (Michel et al. 2011; Chen et al. 2013; Zou et al. 2015; Ganose et al. 2016;
Zhang et al. 2014). All BiOX crystallized in the tetragonal matlockite structure have
layered structure characterized by [Bi2O2] slabs interleaved by double slabs of
halogen atoms. Electrical structures of BiOX were simulated based on density
functional theory (DFT) and the findings are shown in Fig. 2 (Huang and Zhu
2008). Both the valence and conduction bands of BiOX composed of X np
(n = 2–5 for X = F, Cl, Br, and I, respectively), O 2p, and Bi 6p orbitals. The
theoretical measured values of band gap for BiOX (X = F, Cl, Br, and I) were 2.79,
2.34, 1.99, and 1.38 eV, respectively. Comparatively, the experimentally calculated
band gap values were 3.64 (Su et al. 2010), 3.22, 2.64, and 1.77 eV (Zhang et al.
2008), respectively. Both theoretically and experimentally measured results showed
that the band gap of BiOX decreased with an increase in the atomic number of
halogen. Their differences in the band gap values can be due to the limitations
existed within the generalized-gradient approximation (GGA) technique.
A number of approaches have been successfully used for the synthesis of BiOX
with different morphologies and structures (Lin et al. 2007; Zhang et al. 2008; Yu
et al. 2012; Li et al. 2013; Sin et al. 2017). Hydrolysis can be easily done with the use
of simple equipment. It was based on the reaction between soluble bismuth salts and
oxyhalides or H2O. For example, Yu et al. (2012) obtained the pure plate-like BiOX
(BiOCl and BiOBr) nanostructures as efficient photocatalysts quickly and directly
from the hydrolysis of BiX3 (BiCl3 and BiBr3). The BiX3 used in their study can
serve as both bismuth and halogen sources for the synthesis of BiOX. Using the
Fig. 2 Band structures of BiOX: (a) BiOF, (b) BiOCl, (c) BiOBr, and (d) BiOI (Adapted from
Huang and Zhu 2008)
hydrolysis method, Li et al. (2015a) fabricated sheet-like, honeycombed-like, and

flower-like BiOBr by a reaction between BiBr3 with water, ethanol, and isopropyl
alcohol, respectively, at room temperature. The results in their HRTEM analysis also
found that the crystalline facets were varied from (102), (101) to (110), respectively
(Fig. 3). They went further to explain the viscosities of the solvents played important
roles in the growth of BiOBr crystals, which led to different morphologies and
crystalline facets of BiOBr. Under solar light irradiation, sheet-like BiOBr showed
superior photocatalytic activities and stability toward the degradation of methyl
orange. They concluded that the water-based hydrolysis can be carried out simply,
environmental friendly, and energy efficiently, which leads to an ideal technique to
fabricate BiOBr photocatalysts for the practical applications.
Hydrothermal/solvothermal processes were also widely used for the preparation
of BiOX due to their numerous advantages such as low production cost, short
processing time, easily scalable with high yield, environmentally benign, and rela-
tively low temperature synthesis. These processes are usually carried out in an
autoclave (a steel pressure vessel) under controlled temperature and pressure.
The operating temperature is held above the boiling point of the solvent to self-
generate saturated vapor pressure. Zhang et al. (2008) synthesized hierarchical BiOX
(X = Cl, Br, and I) microspheres via a solvothermal route by autoclaving the mixture
of Bi(NO3)3∙5H2O, KCl/NaBr/KI, and ethylene glycol at 160 C for 12 h.
Their findings showed that the synthesized samples exhibited tetragonal phase
spherical-like BiOBr with grain sizes in the range of 1–10 μm. They also added
Fig. 3 TEM and HRTEM images of (a, b) sheet-like BiOBr, (c, d) honeycombed-like BiOBr, and
(e, f) flower-like BiOBr prepared via a hydrolysis method (Adapted from Li et al. 2015a)
Fig. 4 Schematic illustration of formation process of hierarchical BiOX (X = Cl, Br, I) micro-
spheres (Adapted from Zhang et al. 2008)
that the synthesized samples consisted of a large quantity of BiOBr nanoplates and
assembled to construct the hierarchical microspheres with the help of ethylene
glycol. A possible growth mechanism of these hierarchical microspheres has been
proposed and divided into three steps: (1) the formation of BiOX nanoparticles and
their growth into nanoplates at the early stages, (2) ethylene glycol-induced self-
assembly of primary nanoplates to form loose microspheres, and (3) the formation of
regular hierarchical microspheres through a dissolution-recrystallization process
(Fig. 4). Their photocatalytic results showed that all the BiOX products exhibited
higher degradation efficiencies of organic dye as compared to that of TiO2 under
UV-visible and visible light irradiation. Solid state method can also be utilized to
synthesize BiOX. Nevertheless, the requirement of high reaction temperature led to
the synthesized products polluted by metal ions from the reactants and not being
easy purified. Such observation has been reported by Lin et al. (2007) that some Na+
was present in bismuth oxyhalide products prepared via a solid state method. Hence,
the solid state method has barely been utilized recently.
Synthesis of BiFeO3
BiFeO3 (BFO) has attracted a great deal attention owing to its possible applications
as nanogenerators, spintronics, sensors, piezoelectric devices, and ferroelectric
diodes (Bharathkumar et al. 2015; Papadas et al. 2015; Lam et al. 2017). In addition,
band gap of BFO material (~2.2–2.8 eV) is lying in the visible light region of solar
spectrum which extends its horizons to the photovoltaics and photocatalysis areas.
The BFO exhibits multiferroic and ferroelectricity behaviors and has a

rhombohedrally distorted perovskite structure with a space group R3c at room
temperature (Lam et al. 2017). The BFO material shows a Neel temperature of
370 C and a curie temperature of 830 C. A myriad of methods have been
established for the synthesis of nanometer-sized and micrometer-BFO crystallites
including conventional solid-state reaction, coprecipitation, sol–gel process, and
hydrothermal route in literatures (Valant et al. 2007; Wei and Xue 2008; Wang
et al. 2010a; Safi and Shokrollahi 2012).
Using a solvothermal method, Huo et al. (2010) revealed that BFO microsphere
displayed eight times higher photoactivity for the visible light degradation of MB
than that observed for TiO2 (Degussa P25) because of its ability to degrade the
organic pollutants. In another study, Bharathkumar et al. (2015) found that BFO
mesh was able to degrade up to ~98% of the MB dye after 4 h exposure to sunlight
irradiation. They reported that the BFO mesh photocatalysis enhancement was
attributed to the BFO band-bending process and enhanced interaction between the
photocatalyst and dye molecules. This band bending at different band edge positions
created an additional pathway for the transportation of photogenerated e–h+ at the
photocatalyst-dye interface region, leading to the reduction of charge carrier recom-
bination and hence enhanced photocatalytic activity.
For degradation of organic dye solution, dye molecules can absorb visible light
and in some cases their visible light absorption was intense than that of BFO, making
it difficult to determine the photoactivity originated from the photocatalysts. On the
contrary, for the organics without absorbing visible light including 4-chlorophenol
and phenol, the photoactivities of the catalyst were typically studied in the presence
of irradiation above 400 nm (Huo et al. 2011; An et al. 2013; Papadas et al. 2015).
Under reaction conditions (4-chlorophenol concentration = 1.0 104 M; volume
of 4-chlorophenol = 30 mL; reaction time = 4 h), aerosol-spraying prepared BiFeO3
(BFO-2-500) can degrade 4-chlorophenol under the exposure of visible light and
that the photoactivity was superior to those of solid state preparation of BiFeO3
(BFO-SSR) and grinded BiFeO3 (BFO-2-500(G)) (Fig. 5a) (Huo et al. 2011). Huo
and his co-researchers also observed BFO-2-500 (BFO-2-500) can effectively
decompose RhB under visible light irradiation as compared to those of BFO-SSR
and BFO-2-500(G) (Fig. 5b) (Huo et al. 2011).
Nevertheless, in general, it is still inconvenient to prepare BFO compounds
without impurity phases due to the low stability of Bi atom in perovskite BFO and
it is not easy to achieve the structure-controllable BFO with high surface area
(Xu et al. 2016). Additionally, the fabrication of BFO sometimes is based on
complex solution processes and involves toxic precursors (Sakamoto et al. 2008).
Thus, it is indispensable to employ an environmental-friendly method to produce the
pure BFO photocatalyst.
Stability and reusability of the catalyst need to be comprehensively studied
before being devoted into practical applications. Papadas et al. (2015) showed
that BFO 3D mesoporous network not only can be reused for three catalytic runs
but can also be recovered easily from the 4-nitrophenol mixture using an external
magnet (Fig. 6). The recovering process of catalyst from the reaction medium is
a
BFO-2-500
20
Degradation yield (%)

15
10
BFO-2-500(G)
BFO-SSR
5
No catalyst
0
Photocatalyst
b 100
80
Light off Light on

60
C/Co
40
No catalyst
BFO-SSR
20 BFO-2-500(G)
BFO-2-500
0
-1 0 1 2 3 4 5 6
Time (h)
Fig. 5 (a) Degradation of RhB solution in the presence of solid state prepared BFO (BFO-SSR)
and grinded BFO (BFO-2-500(G)), aerosol-spraying prepared BFO (BFO-2-500) nanoparticles
under visible light irradiation (λ > 420 nm) and (b) photodegradation of 4-chlorophenol over solid
state preparation of BFO-SSR and grinded BFO-2-500(G), BFO-2-500 nanoparticles under visible
light irradiation for 4 h (Adapted from Huo et al. 2011)
another important factor for their practical applications. According to the

abovementioned discussion, BFO owned magnetically attractive property and
thus it was found to be relatively easier to filter from the mixtures. Nevertheless,
the photocatalytic performance of durable use and lifetime of the BFO still
presence of data shortage which required further investigation. Also, the safety of
BFO photocatalyst has no report yet. In general, the Bi, Fe, and O elements are
bonded in a form of perovskite-type material with thermal and chemical treatments,
and hence, the photocatalysts should be focused on safety issue of human and
environment.
Fig. 6 Catalytically 1.0

recyclable degradation of 4- 1st run 2nd run 3rd run
nitrophenol by BFO 3D
mesoporous network with 0.8
inserted isolation of the
catalyst using an external
0.6
magnetic field (Adapted from
At/Ao
Papadas et al. 2015)
0.4
0.2
0.0
0 100 200 0 100 200 0 100 200 300
Time (s)
Fig. 7 Crystal structures of (a) HBIP, (b) nMBIP, (c) mMBIP (Adapted from Pan et al. 2011)
Synthesis of BiPO4
Bismuth orthophosphate (BiPO4) demonstrated many advantages as photo-
catalysts such as excellent photocatalytic activity, exceptional optical and elec-
tronic properties, high mineralization ability, stable chemical structure, and fast
rate of settlement separation. It is recognized to have three crystal structures:
hexagonal phase (HBIP, space group: P3121), monoclinic phase (nMBIP, space
group: P21/n), and monoclinic phase (mMBIP, space group: P21/m) as indicated
in Fig. 7. The structure of BiPO4 can be simply described by one bismuth
atom surrounded by eight oxygen atoms as well as one phosphate atom
surrounded by four oxygen atoms. Among these crystal structures, HBIP with
a band gap of 4.6 eV exhibited the lowest photocatalytic activity. Both the
nMBIP and mMBIP demonstrated higher photocatalytic activity and their band
gap were determined to be 3.8 eV and 4.2 eV, respectively (Li et al. 2011; Pan
et al. 2011; Pan and Zhu 2015).
BiPO4 photocatalyst was firstly prepared by Pan and Zhu (2010) via a hydro-
thermal process between Bi(NO3)3.6H2O and Na3PO4•12H2O for the degradation of
organic dyes. Their results showed that the synthesized BiPO4 was a promising
UV-responsive photocatalyst and its photocatalytic activity was about twice higher
than that of the well-known Degussa P25 (Fig. 8a). Both the high position of valence
band and the high e–h+ pair separation efficiency led to the high photocatalytic
activity of BiPO4. They also added that the inductive effect of PO43 played an
important role in assisting the e–h+ pair separation. Subsequently owing to its low
cost, nontoxicity, and high photoefficiency, BiPO4 has been widely documented for
the environmental purification. A facile and rapid microwave irradiation method has
also been used for the synthesis of BiPO4 nanostructures as active photocatalysts for
methyl orange degradation under UV-visible irradiation (Li et al. 2011). By varying
the solvents, different morphologies of BiPO4 nanostructures such as rice-like,
nanoparticles, nanorods, nanoneedles have been synthesized. Their proposed for-
mation mechanism of BiPO4 nanostructures was a diffusion-controlled process in
organic solvents, which greatly ascribed to variation of diffusion rate and concen-
tration of monomer in different solvents (Fig. 8b). In addition to degradation of
organic pollutants from aqueous solution, BiPO4 has been reported as photocatalysts
for the conversion of gas phase benzene into CO2. Nevertheless, BiPO4 has poor
visible light absorption due to its wide band gap and thus limiting its practical
widespread application.
Fig. 8 (a) Photocatalytic

kinetic constants on the
degradation of methyl orange,
rhodamine B, and
4-chlorophenol over BiPO4
and P25 (Adapted from Pan
and Zhu 2010). (b) Schematic
illustration of formation
mechanism of BiPO4
nanostructures synthesized in
different solvents (Adapted
from Li et al. 2011)
Photocatalyst Modification and Doping
To absorb larger fractions of the solar spectrum for photocatalysts, numerous

material engineering solutions have been developed such as morphology control,
doping, heterojunction structures, and combining the carbon materials (Li and Yan
2009; Li et al. 2013; Park et al. 2013; Li et al. 2014a; Fan et al. 2015; Meng and
Zhang 2017). The basis in using these material engineering strategies is to balance
both the half-reaction rates of the photocatalysis by modifying the catalyst structure
and composition as well as adding electron acceptors. By using these methods, either
the charge carrier separation of photocatalyst or solar light harvesting can be
effectively improved, which thus enhanced the photocatalytic performance.
A lot of research works have been performed in order to gain optimum morphol-
ogies and crystal structures that are competent of improving the visible light
photoactivity of photocatalyst powders. Rhombohedral BFO powders synthesized
by a PVP-assisted hydrothermal route at 180 C for 72 h in the presence of different
alkaline conditions obtained different morphologies: spindle-like structures (0.5 M
NaOH), cube-like particles (2 M NaOH), and plate-like structures (4 M NaOH)
(Huang et al. 2014). The formation of the different BFO structures was owing to
the crystal facets matching as shown in their XRD patterns and HRTEM images.
The photoactivity of the BFO plates with (104) facets exposed was the best among
the three photocatalysts for visible light degradation of MO. Using microwave
synthesis, Li et al. (2012) observed 3D flower-like BiOBr nanostructures possessed
large surface area and exhibited excellent removal capacity and fast adsorption rate
for Cr(VI) ions in a wide pH range.
Owing to the great difference in intrinsic features of distinct elements, searching
proper dopants for a certain photocatalyst also played a key role in enhancing the
photocatalytic performance. Yin et al. (2011) have systematically studied the prop-
erties of metal-doped BiVO4 by using first-principles density functional theory
(DFT), which indicated that monoclinic BiVO4 with minimized photo-generated
carrier recombination could be achieved by doping Br, Ca, Na, or K at O-rich growth
conditions or Mo, W at O-poor growth conditions. Remarkable enhanced photo-
activity of W, Mo, Co, or Cu doped BiVO4 has also been found by experiments (Yao
et al. 2008; Parmer et al. 2012; Park et al. 2013). In addition, research works on
nonmetal doping bismuth-related semiconductors have garnered much attention.
Zhang and Zhang (2010) revealed self-doping BiOIs with I/Bi molar ratio varying
from 1 to 3. Their experimental results as well as DFT calculations revealed that
iodine self-doping could efficiently alter the BiOI optical absorption property.
Their photocatalytic activities were tested by degradation of MO and removal of
nitric oxide. 1.5 of I/Bi ratio was found to be the best. Improved photoactivity has
also been demonstrated in F-doped BiVO4 and F-doped Bi2WO6 (Fu et al. 2008;
Jiang et al. 2013).
In the photocatalytic reaction, heterojunction was established when the band
gaps of two semiconductor materials were overlapped and thus e–h+ can be
transferred in direct migration from one level to another with the existence of
noble metallic (e.g., Au, Pd, Pt, and Ag) or conducting interface. Li et al. (2015b)
reported that Ag@AgCl anchored on (040) crystal facet BiVO4 (Ag@AgCl/

BiVO4) was a visible light-responsive photocatalyst in which the metallic Ag
species not only act as the solid-state electron mediator but can also absorb the
photons from incident light and present the surface plasmon resonance (SPR)
effect (as illustrated in Fig. 9a). This process could decrease the recombination
of charge carriers and thus improved the photoactivity in the visible light degra-
dation of RhB (Fig. 9b). As shown in Fig. 9c, under visible light irradiation, BiVO4
and metallic Ag could be excited. Metallic Ag can act as a bridge transporting e
from its conduction band minimum (CBM) to CBM of AgCl, while photo-
generated e in CBM in BiVO4 will migrate to the metallic Ag to facilitate the
e–h+ separation in AgCl and BiVO4 alone. Novel Ag/AgBr/BiOBr hybrid with
superior visible light–driven photocatalytic activities in sterilization of pathogenic
organism and degradation of organic dye has also been reported by Cheng et al.
(2011). Besides applying a noble metal heterojunction, the utilization of a semi-
conductor heterojunction can also act as an efficient photocatalyst system with
promising visible light activity. Ren et al. (2011) fabricated a heterostructured
photocatalyst containing the same Bi, Mo, and O elements (Bi3.46Mo0.36O6/
Fig. 9 (a) UV–vis diffuse reflectance spectra of the BiVO4, Ag/BiVO4, Ag@AgCl/BiVO4, and
AgCl materials, (b) photocatalytic degradation of RhB in the presence of different photocatalysts
under visible-light irradiation, and (c) schematic diagram illustration of Z-scheme mechanism
photodegradation of RhB dye over Ag@AgCl/BiVO4 heterostructure photocatalyst under visible
light irradiation (Adapted from Li et al. 2015b)
Bi2MoO6). The as prepared samples could efficiently mineralize organic sub-

stances into CO2 under exposure of visible light, which was owing to high
e–h+ pair separation between the heterojunction interfaces. Consistent reports
including BiOI/BiOBr, Bi2O3/Bi2MoO6, BiVO4/Bi2O3, Bi2O3/Bi2WO6, Ag2O/
Bi2MoO6, Ag3PO4/Bi2MoO6, Bi2S3/BiOI, and AgI/BiOI have also been found
in the literatures (Li and Yan 2009; Cao et al. 2011; Gui et al. 2011; Cao et al.
2012a, b; Xu et al. 2013; Meng and Zhang 2017).
As for carbon materials, they have a great potential in a large variety of
environmental clean-up applications owing to their outstanding characteristics
of corrosion resistance, strong thermal stability, large surface area, and good
electronic properties. Earlier reports have stated that the carbon material–semi-
conductor material junctions can hinder the e–h+ recombination as well as
enhance the pollutants adsorption capacity on the composite, leading to the
improvement of photoactivity. It was reported that the photoactivity can be
improved when BiFeO3 coupled with graphene (GR) (Li et al. 2013, 2014a)
and graphitic carbon nitride (g-C3N4) (Fan et al. 2015). Other bismuth-related
materials such as BiOBr (Zhang et al. 2012), Bi2O3 (Wang et al. 2010b),
and Bi2O2CO3 (Madhusudan et al. 2012) have also been successfully composited
with graphene.
Supported Photocatalysts
In catalyst-based photocatalysis technologies, agglomeration of nano-sized photo-

catalysts is one of the main reasons to use a support material (Lam et al. 2010).
Many types of porous materials such as zeolite, carbon, silica, and others have
been then investigated as photocatalyst supports in the photodegradation of
numerous organic pollutants (Pozzo et al. 1997). These support photocatalysts
are essential to be in micro or as mesoporous catalyst to facilitate easily particle
separation from the fluids (liquid or gaseous) and enable them to be packed inside
a vessel with fluids moving through the reactor system. Nevertheless, it is required
to strongly anchor the nano-sized photocatalyst to the surface, for instance,
functional groups bonding to the surface or defect sites on the surface and
photocatalyst itself (Stevensa et al. 2005; Sebastian et al. 2010). The agglomera-
tion can still take place if the nano-sized photocatalysts is not strongly deposited
on the surface of the supports.
Another merit of support photocatalysts are concerned on the porosity and surface
area with respect to the adsorption of the organic pollutant on the photocatalyst
surface. It seems clear that a large surface area provided by accessible pores is crucial
for concentrating the target pollutant around the active photocatalyst. Consequently,
the direct oxidation of h+ could be the main oxidation pathway since the adsorption
of organic pollutants on the semiconductor surface was the prerequisite step
for direct charge carrier transfer. Alternatively, direct oxidation by •OH radicals
required the adsorption of water or OH ions on the catalyst surface to produce the
•OH radicals.
Multivariate Analysis
Despite catalyst-based photocatalysis is an emerging technology utilized for the

degradation of persistent compounds in the last few decades, some reports revealing
on the statistical design of experiment (DOE) application toward the photocatalytic
process are available (Lam et al. 2012; Callao 2014). Multivariate analysis is one of
these statistical DOE approaches, which helps to account for interaction effects
between the studied variables and determine more accurately the combination of
levels that produces the optimum of the process. By comparing with the traditional
one-factor-at-a-time (OFAT) or univariate approach, one variable involved in the
photodegradation is varied, while holding the others variables constant. Moreover,
the result of this univariate analysis indicates insufficient optimization toward
response(s). In this regard, the OFAT approach is costly in sense of time and reagents
and not that efficient. There is now increasing exploration of process optimization
using experimental field, where it can be analyzed using commercial statistical
software such as SAS, Minitab, and Design Expert.
The first step during the development of this analysis is the selection of appro-
priate response(s) or output(s) since it should take into account the sources of error,
ways of minimizing it, and of course the ability to follow the change in response(s) in
course of time. For instance, the possible response(s) could be percent of degradation
and decolorization rate or even degree of mineralization of the sample. On the
contrary, variables that influence the response could be photocatalyst synthesis
factors such as dopant content, heating temperature, photocatalyst dose, surfactant
amount, or operation factors such as initial concentration of target compound, pH,
light irradiance, and electron acceptors. The key of DOE is based on the selection of
the experimental points at which the response could be examined. The selection of
appropriate DOE have a great impact on the constructing of response surface and
hence its accuracy on the prediction.
Abdullah et al. (2012) proposed the use of central composite design (CCD)-DOE
approach together with analysis of variance, statistical regression, and response
surface analysis to study the combined effects of three key operation variables that
affect the visible light photocatalytic removal using BiVO4. They utilized 3 experi-
mental variables to analyze the 51 possible variables combination. It was reported
that the interaction between the photocatalyst dose and solution pH had a positive
synergistic effect on the overall removal rate. A response surface model was created
to correlate the removal rate dependency on the three different variables according to
the statistical regression as shown in Eq. (1):
X XX XX X
Y ¼ b0 þ bi X i þ bij Xi Xj þ bijk Xi Xj Xk þ e (1)
ij jk
where Y is the predicted response; i, j, and k take values from the number of
parameters; b0 is the constant; bi represents linear coefficient; and bij and bijk are
quadratic and cubic coefficients where i = j and i = j = k, respectively. These refer to
interactions of first or second order, respectively, Xi, Xj, and Xk are the levels of
independent parameters and e is the random error. This model (Eq. 1) is empirical
and independent for each photocatalytic system. The following verification works
are required to measure the accuracy and applicability of such model for the
prediction of photoreaction rate under the variation of its variables. Other DOE
approach to photocatalytic system optimization has also been applied over the years
such as factorial design, Box–Behnken design, and Taguchi design (Mera et al.
2016, 2017; Xiao et al. 2017).
Energy Consumption and Economic Analysis
Although several studies are available in the literature on electrical energy determi-
nation of a variety of photocatalysis processes, it is essential to evaluate the electrical
energy consumption and economic analysis of the photocatalysis under experimental
conditions. Typically, the electrical energy consumption of photocatalysis governs
by a number of experimental factors (type of pollutant being treated, configuration of
the reactor, and type of light source used, etc.) and thus, electrical energy determi-
nation becomes crucial for the processes investigation. A number of factors includ-
ing economics, effluent quality, cost, etc. also show a vital role in selecting a
wastewater treatment technology. In literatures, the study of energy consumption
and economic analysis of bismuth-based photocatalysts was scarcely reported.
Hence, the following section is focusing on the photocatalysts which are typically
found in the literatures.
Electrical Energy Determination
Since the photocatalytic visible light degradation process is an electrical energy

intensive process, the electrical energy denotes a major fraction of the operating
costs. The figures-of-merit based on electrical energy per order (EEo) can be infor-
mative and useful as they allow for a rapid determination of the electrical energy
cost. The EEo is defined as the number of kilowatt hours of electrical energy required
to reduce the concentration of pollutant by 1 order of magnitude in a unit volume of
contaminated water. The EEo (kWh/m3/order) can be obtained from the following
Eq. (2).
P t 1000
EEo ¼ (2)
Ci
V 60 log
Cf
where P is the input power (kW), t is the irradiation time (min), V is the volume of
water (L ) in the reactor, and Ci and Cf are the initial and final pollutant concentra-
tions, respectively. This equation is implicitly related to the Langmuir-Hinshelwood
(L-H) model first-order kinetics as shown in Eq. (3).

Ci
In ¼ kapp t (3)
Cf
By combining the Eq. (3) and the L-H first-order kinetics, the EEo can be
expressed as shown in Eq. (4).
3:84 P
EEo ¼ (4)
V kapp
Typical EEo for a range of organic pollutants is provided in Table 1. EEo makes the
scale-up and comparison of relative treatment performance very simple. For exam-
ple, from Table 1, 4-nitrophenol has an EEo of 72.3 kWh/m3∙order, while Acid Red
27 has EEo of 12.6 kWh/m3∙order (Behnajady et al. 2011). Acid Red 27 requires 5.7
times more energy for the same level of degradation as 4-nitrophenol. Thus, under
similar influent and effluent conditions, the treatment system for Acid Red27 would
require five times the UV power of that treating 4-nitrophenol in the photocatalytic
system.
Total Operating Cost
Cost evaluation is one of the most pivotal characteristics in water treatment.

The overall costs can be indicated by the sum of the capital cost, operating cost,
and maintenance cost. For conventional water and wastewater treatment systems,
these costs strongly depend on the nature, concentration of pollutant, and the
configurations of the reactor used. Thus, the cost evaluation was performed on
the basis of the EEo determined for the entire experimental runs. The total
operating cost for the photodegradation of organic pollutants is demonstrated in
Eqs. (5) and (6).
Totaloperationcost ðUSD=kgÞ
Totalenergy consumedper mg of pollutant removal ðkWhÞ
USD (5)
Unit cost of power 106
kWh
¼
pollutant removal ðmgÞ
Totalenergy consumed per mg of pollutant removal ðkWhÞ

Powerinput ðkWÞ Reactiontime ðminÞ
¼ (6)
1000 60
It must be highlighted again from Table 1 that the reported studies have been
conducted on photocatalytic degradation of organic pollutants using different
experimental conditions with respect to, for instance, pH, temperature, and so
on could strongly influence the obtained total operating cost values (Pujara et al.
2007; Benotti et al. 2009; Mehrjouei et al. 2013; Mahamuni and Adewuyi 2010).
Table 1 Evaluate of the electrical costs of the organic pollutants degradation
Concentration Reactor Light Power input kapp EEO
69
Organics (mg/L) type Catalyst source (w) (min1) (kWh/m3order) References
Rhodamine 50 Slurry Si-doped UV-visible 150 4.32 8.00 1010 Xie et al. (2010)
TiO2
10 Thin film TiO2-coated UV 10 3.42 1.12 104 Li et al. (2014b)
beads
25 Thin film H3PW12O40/ Visible 300 18.00 1.92 1010 Lu et al. (2012)
TiO2
Methylene blue 44 Slurry CdS Visible 300 0.033 6.99 103 Lin et al. (2008)
nanosphere
10 Slurry CdS/ZnS Visible 500 0.5 1.17 103 Forgacs and Cserhati
(2004)
27 Slurry Degussa TiO2 UV 125 0.053 1.21 102 Lachheb et al. (2002)
3 Slurry CdS LED 3 0.0212 1.58 102 Repo et al. (2013)
Methyl orange 15 Thin film TiO2/ZnO/ UV-visible 300 11.55 3.59 1010 Zhu et al. (2012)
chitosan
8.17 Slurry Y-TiO2-ZSM UV 120 10.60 1.56 1010 Okte and Yılmaz
(2008)
10 Thin film TiO2-coated UV 10 2.59 1.48 104 Li et al. (2014b)
bead
10 Slurry TiO2 UV 15 0.12 34.8 Behnajady et al.
Malachite green 5 nanoparticles 0.62 9.23 (2011)
Acid Red 27 20 0.46 12.6
Advancement of Photocatalytic Water Treatment Technology for. . .
4-Nitrophenol 20 0.4 72.3

Phenol-4- 80 Slurry Degussa TiO2 UV (one 39.5 0.03a 39.9 Pujara et al. (2007)
sulfonic acid unit)
UV (two 79 0.13a 18.4
units)
UV (three 118.5 0.42a 85
units)
1735
a
log((TOC)i/(TOC)f)
Similarly, conducting the real wastewater treatments can also alter these values,
depending on the pollutant contents in the wastewater.
Photocatalytic Disinfection in Water
The effectiveness of the photocatalysis technology in antimicrobial was first dem-

onstrated by Matsunaga et al. (1985), who reported that the Lactobacillus acidoph-
ilus, Saccharomyces cerevisiae, and Escherichia coli were completely sterilized
under metal halide lamp irradiation for 60–120 min. By far, most of the investiga-
tions were focused on the Gram-negative bacterial model Escherichia coli.
For example, enhanced photocatalytic bacteriostatic activity toward Escherichia
coli has been reported by Wang et al. (2016) via the visible-light driven BiOI/
BiOBr hierarchical microspheres. Their studies on the determination of cell structure
destruction and the release of K+ proved the rupture of cell membranes during the
photocatalysis. They also added that the h+ is the major species on the photocatalytic
disinfection of Escherichia coli. Recently, Ahmad et al. (2016) reported that
the death of Escherichia coli cells over BiOBr was due to the •OH radicals that
formed during photocatalysis. The attack of •OH radicals led to the oxidation of
functional groups in the cell membrane and interrupted the membrane permeability.
This can lead to the leakage of intracellular substances, demolition of microbial
structure, and ultimately the inactivation of Escherichia coli. In addition to
Escherichia coli, a wide range of microorganisms including fungi, viruses, and
many types of bacteria were also successfully inactivated by photocatalytic
treatment.
Water Quality
The constituents in wastewater can be derived from domestic, municipal, and

industrial sources such as bath water, food waste, human excreta, personal and
household maintenance products along with a broad range of other inorganic
and organic compounds in trace amounts. Given a vast diversity of constituents
that may be observed in the wastewater, it is common practice to characterize the
water quality parameters in the wastewater. The following discussion is introduced
on the water source of different qualities which is scarcely of concern in the catalyst-
based photocatalysis.
Turbidity
Turbidity is a measure of water clarity. This parameter is an integrated measurement

of the extent to which light is either absorbed or scattered by the suspended and
dissolved particulates in the water. The turbidity may be caused by a wide variety of
causes. For instance, the turbidity may be caused by glacier-fed rivers and lakes,
rivers descend from mountain areas and plains, rivers under flood conditions, and
rivers moving toward the ocean. In particular, as rivers moving toward the ocean,
they pass through the urban areas where the industrial and domestic wastewaters
treated or untreated may be added. The industrial wastes may include a huge q

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With 811 Figures and 417 Tables

ISBN 978-3-319-73644-0 ISBN 978-3-319-73645-7 (eBook)

© Springer Nature Switzerland AG 2019

Environmental management is the management of the interaction and impact of

Chaudhery Mustansar Hussain, Ph.D.

Part I Major Environmental Issues and Problems .............. 1

1 Assessment of Some Aspects of Provisioning Sewerage

9 Fluoride Contamination in Groundwater and the Source

10 Identiﬁcation of the Source Mineral Releasing Arsenic in the

11 Industrial Solid Waste Management in a Developing Country

12 Indoor Air Pollution Around Industrial Areas and Its Effect:

13 Scenario of Landﬁlling in India: Problems, Challenges, and

14 Environmental Health Problems Due to Air Pollution

15 Microplastics as Contaminant in FreshWater Ecosystem:

16 Impact of Material Chemistry on the Performance

Part II Environmental Site Remediation . . . . . . . . . . . . . . . . . . . . . 415

17 Technologies for Treatment of Colored Wastewater from

18 Application of Novel Microbial Consortia for Environmental

Part III Hazardous Waste Management . . . . . . . . . . . . . . . . . . . . . . 617

24 Development of an Environmentally Sustainable Approach

27 Management of Hazardous Paper Mill Wastes for Sustainable

28 Management of Municipal Solid Waste in Morocco: The Size

29 Hazardous Waste Management with Special Reference to

Part IV Management of Radioactive Wastes . . . . . . . . . . . . . . . . . . 741

30 Management of Radioactive Wastes . . . . . . . . . . . . . . . . . . . . . . . 743

31 Actinide Speciation in Environment and Their Separation

Part V Management of Special Wastes: CO2, CH4, NOX, SO2,

32 Prospects and Issues of Phosphorus Recovery as Struvite from

33 Global Status of Nitrate Contamination in Groundwater:

34 Remediation of Industrial and Automobile Exhausts for

35 Management of Residues from Air Pollution Control

Part VI Environmental Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 927

36 Tailor-Made Molecular Traps for the Treatment of

46 Characterizing the Cell Surface Properties of

47 Preparation, Characterization, and Heavy Metal Ion Adsorption

48 Concept Note on Method Development for Speciation and

49 Determination of Select Heavy Metals in Air Samples from

50 Recent Advances in Membrane Extraction Techniques for

51 Environmental Toxicology and Air Pollution: A Comparative

52 The Effects of Atmospheric Pollution in Respiratory Health . . . . 1271

Part VII Environmental Treatment Technologies . . . . . . . . . . . . . . 1287

53 Advanced Treatment Technologies . . . . . . . . . . . . . . . . . . . . . . . . 1289

54 Treatment of Domestic Gray Water by Multicomponent

55 Development In-House: A Trap Method for Pretreatment of Fat,

56 Environmental Treatment Technologies: Adsorption . . . . . . . . . . 1367

57 Making Artiﬁcial Beachrock Through Bio-cementation:

58 Potential of Biogas Technology in Achieving the Sustainable

59 A Review on Treatment of Pharmaceuticals and Personal

60 Constructed Wetland: A Green Approach to Handle

61 How to Improve Selectivity of a Material for Adsorptive

62 Advanced Pretreatment Strategies for Bioenergy Production

63 Green Infrastructure: Cost-Effective Nature-Based Solutions

64 The Modiﬁed Bardenpho Process . . . . . . . . . . . . . . . . . . . . . . . . . 1551

65 Diagnostic and Treatment by Different Techniques of Leachates

66 Application of Liquid Chromatography-Mass Spectrometry for

67 Olive Mill Wastewater: Treatment and Valorization

Part VIII Environmental Management of Biomaterials ......... 1899

77 Sustainable Biomedical Waste Management . . . . . . . . . . . . . . . . 1901

78 Agrowaste Materials as Composites for Biomedical

Part IX Environmental Modeling (Mathematical Modeling

79 A New Method to Estimate the Instantaneous NOx Emissions

Part X Environmental Nanotechnology: Management of

84 Nano-wastes and the Environment: Potential Challenges and