Integrated Environmental Technologies

for Wastewater Treatment and

Sustainable Development - eBook PDF
Visit to download the full and correct content document:
https://ebooksecure.com/download/integrated-environmental-technologies-for-wastew
ater-treatment-and-sustainable-development-ebook-pdf/
 INTEGRATED
ENVIRONMENTAL
TECHNOLOGIES
FOR WASTEWATER
TREATMENT AND
SUSTAINABLE
DEVELOPMENT
 INTEGRATED
ENVIRONMENTAL
TECHNOLOGIES
FOR WASTEWATER
TREATMENT AND
SUSTAINABLE
DEVELOPMENT
Edited by

Vineet Kumar
Waste Re-processing Division, CSIR-National Environmental Engineering
Research Institute (CSIR-NEERI), Nehru Marg, Nagpur,
Maharashtra-440020, India

Manish Kumar
CSIR-National Environmental Engineering Research Institute
(CSIR-NEERI), Nehru Marg, Nagpur, Maharashtra-440020, India
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States

Copyright © 2022 Elsevier Inc. All rights reserved.

No part of this publication may be reproduced or transmitted in any form or by any means, electronic
or mechanical, including photocopying, recording, or any information storage and retrieval system,
without permission in writing from the publisher. Details on how to seek permission, further
information about the Publisher’s permissions policies and our arrangements with organizations such
as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website:
www.elsevier.com/permissions.
This book and the individual contributions contained in it are protected under copyright by the
Publisher (other than as may be noted herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and experience
broaden our understanding, changes in research methods, professional practices, or medical treatment
may become necessary.

Practitioners and researchers must always rely on their own experience and knowledge in evaluating
and using any information, methods, compounds, or experiments described herein. In using such
information or methods they should be mindful of their own safety and the safety of others, including
parties for whom they have a professional responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume
any liability for any injury and/or damage to persons or property as a matter of products liability,
negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas
contained in the material herein.

ISBN: 978-0-323-91180-1

For Information on all Elsevier publications visit our website at

https://www.elsevier.com/books-and-journals

Publisher: Susan Dennis

Editorial Project Manager: Judith Clarisse Punzalan
Production Project Manager: Bharatwaj Varatharajan
Cover Designer: Mark Rogers

Typeset by Aptara, New Delhi, India

 Dedication

Dedicated to my teachers, and mentors, from whom I continue to learn, and to my family for
their support, blessings, motivation, and love.
Vineet Kumar

Dedicated to my family especially my wife without whose support this book would not have
been possible.
Manish Kumar
 Contents

Contributors xv 2. Anaerobic ammonium oxidation

About the editors xxi (anammox) technology for nitrogen
Preface xxiii removal from wastewater: Recent advances
and challenges 23
Acknowledgments xxvii
Himani Chandel, Kirti Shyam, Navneet Kumar, Geetansh Sharma,
Manu Yadav, Sibiraj Murugesan, Saurabh Thakur and Gaurav Saxena
1. Integration of photocatalytic and
biological processes for treatment of 2.1 Introduction 23
complex effluent: Recent developments, 2.2 Microbiology of anaerobic ammonium
trends, and advances 1 oxidation (anammox) 25
2.3 Techniques for enrichment of anammox 28
Govindaraj Divyapriya, Lakshmi Pisharody, Ansaf V. Karim and
Puthiya Veetil Nidheesh
2.3.1 Anammox enrichment in batch
experiments 28
1.1 Introduction 1 2.3.2 Anammox enrichment in bioreactor
1.2 Biological treatment of organic systems 29
contaminants 3 2.3.3 Sequencing batch reactor (SBR) 29
1.2.1 Activated sludge process 4 2.3.4 Upflow anaerobic sludge blanket
1.2.2 Anaerobic digestion 4 (UASB) reactor 29
1.2.3 Trickling bed filter/bioreactor 5 2.3.5 Upflow biofilter (UBF) 30
1.2.4 Membrane bioreactor 5 2.4 Molecular methods for identification of
1.2.5 Moving bed biofilm reactor 5 anammox 30
1.3 Photocatalytic degradation of organic 2.4.1 Polymerase chain reaction followed
contaminants 6 by denaturing gradient gel electrophoresis
1.4 Need for integrated process for treatment of (PCR-DGGE) 30
complex effluent 7 2.4.2 Denaturing gradient gel electrophoresis
1.5 Combined photocatalysis and biological (DGGE) 31
process 8 2.4.3 Fluorescent in situ hybridization 31
1.5.1 Photocatalysis as pretreatment 9 2.4.4 Real-time polymerase chain reaction 32
1.5.2 Photocatalysis as post-treatment 12 2.5 Preservation of anammox 32
1.5.3 Multistep processes 13 2.6 Carriers and their effects on anammox 32
1.6 Mineralization and toxicity reduction 14 2.7 Application of anammox in wastewater
1.7 Pilot-scale integrated process 15 treatment 33
1.8 Conclusion 16 2.8 Factors affecting treatment performance of
References 16 anammox 36
2.8.1 pH 36

vii
viii Contents

2.8.2 Temperature 36 4.3 Integrated strategies for simultaneous

2.8.3 Effect of substrate concentration 36 production of SCO and biological treatment
2.8.4 Dissolved oxygen (DO) of wastewaters by oleaginous microorganisms 85
concentration 37 4.3.1 Wastewaters as substrates of oleaginous
2.8.5 Organic matter 37 microorganisms 86
2.8.6 Sludge retention time 37 4.3.2 Oleaginous microorganisms employed
2.9 Integration of anammox into other for simultaneous wastewater treatment
remediation technologies for and SCO production 86
effective wastewater treatment 37 4.3.3 Industrial application of the
2.10 Challenges and future prospects for wastewater treatment by oleaginous
anammox research 39 microorganisms: advantages,
2.11 Conclusion and recommendations 40 technology, strategies, problems,
References 40 and perspectives 93
4.4 Conclusions 96
3. Integrated process technology for Acknowledgments 97
recycling and re-use of industrial and References 97
municipal wastewater: A review 49
Yeit Haan Teow, Kah Chun Ho, Sumith Ranil Wickramasinghe,
Mahmood Gheni Jebur and Zhen Hong Changa
5. Nature-inspired ecotechnological
approaches toward recycling and recovery of
3.1 Introduction 49 resources from wastewater 101
3.2 Wastewater treatment technologies 54
Jayanta Kumar Biswas, Monojit Mondal, Vineet Kumar,
3.2.1 Differences between industrial and Amit Bhatnagar, Soma Biswas and Meththika Vithanage
municipal wastewater 55
3.2.2 Classes of treatment processes 56 5.1 Introduction 101
3.3 Integrated processes: examples and benefits 61 5.2 Living technologies: borrowing ideas
3.4 The future of water reuse opportunities 65 and inspiration from Mother Nature 103
3.4.1 Potable usage 65 5.3 Genesis of the concept of “living
3.4.2 Nonpotable usage 66 machines” 104
3.5 Conclusion 70 5.4 Trademark tenets of living technologies:
Acknowledgments 71 ten commandments (wisdom) of Mother
References 71 Nature mark the hallmarks 106
5.5 Applications of living technologies:
4. Integrated production of biodiesel and Mother Nature’s Midas touch for
industrial wastewater treatment by culturing transforming waste(water) into wealth 107
oleaginous microorganisms 81 5.6 Designing traits for trading natural
wastewater treatment systems 107
Silvana Carolina Viñarta, Débora Daniela Maza,
5.7 Tools of the trade 112
Pablo Marcelo Fernández, Manuel Javier Aybar
and Lucía Inés Castellanos de Figueroa 5.7.1 Floral components: the solar-based
photosynthetic foundations 112
4.1 Alternative energy sources: biodiesel 81 5.7.2 Faunal diversity 113
4.1.1 Oleaginous microorganisms 82 5.8 Variants of living technological systems 113
4.1.2 Lipogenesis in oleaginous 5.8.1 Floating treatment wetlands 113
microorganisms and more important 5.8.2 Integrated waste stabilization ponds
aspects of lipid accumulation 82 train system 121
4.2 Substrates for SCO production by oleaginous 5.8.3 Constructed wetlands:
microorganisms 84 phytomicroremediation in
4.2.1 Low-cost substrates for SCO Nature’s image 125
production 85 5.8.4 Hydroponics: soilless cultivation 129
 Contents ix

5.8.5 Wastewater-fed aquaculture: 7.4 Mechanisms involved 179

a win–win way to waste 7.4.1 Dissolution precipitation 179
into wealth? 133 7.4.2 Ion exchange 181
5.9 Conclusions 135 7.4.3 Physical adsorption 182
References 136 7.4.4 Electrostatic interactions 182
7.5 Recent trends in wastewater treatment
6. Integrated microbial desalination cell with HAP 182
and microbial electrolysis cell for wastewater 7.6. Conclusion and future perspectives 183
Acknowledgments 184
treatment, bioelectricity generation, and
References 184
biofuel production: Success, experience,
challenges, and future prospects 145 8. Algae coupled constructed wetland
Mohammed Al-Murisi, Dana Al-Muqbel, Amani Al-Othmana and system for wastewater treatment 191
Muhammad Tawalbeh Akanksha Chauhan and Sanjeev Kumar Prajapati

6.1 Introduction 145 8.1 Introduction 191

6.2 Microbial electrolysis cells (MECs) 146 8.2 Constructed wetlands in wastewater system 192
6.2.1 MEC for wastewater treatment and 8.2.1 Classification 193
hydrogen production 148 8.2.2 Design parameters 196
6.2.2 Integration MEC with other systems 149 8.2.3 Removal efficiency 198
6.2.3 MEC for the production of valuable 8.2.4 Limitations with constructed wetlands
products 151 in wastewater treatment 199
6.3 Microbial desalination cells (MDCs) 153 8.3 Algae in wastewater treatment 200
6.3.1 Optimized MDC systems for 8.3.1 Cultivation system for algae-mediated
wastewater treatment, salinity wastewater treatment 201
removal and power generation 153 8.3.2 Limitation with algae-mediated
6.3.2 Integrated MDC systems 156 wastewater treatment 202
6.3.3 MDC for the production of 8.4 Algae coupled constructed wetland 202
valuable products 158 8.4.1 Removal of nutrients 203
6.4 Challenges and limitations 159 8.4.2 Removal of organics 203
6.4.1 MEC challenges 159 8.4.3 Removal of emerging contaminants 204
6.4.2 MDC challenges 160 8.4.4 Challenges with algae coupled
6.5. Conclusions and future perspectives 161 constructed wetland 204
References 162 8.5 Resource and energy recovery through
algae coupled constructed wetland 204
7. Hydroxyapatite for environmental 8.6 Real-world application of algae coupled
remediation of water/wastewater 167 constructed wetland: perspectives 205
Pabasari Arundathi Koliyabandara, Oshadi Hettithanthri,
8.7 Conclusion and future prospects 205
Anushka Rathnayake, Anushka Upamali Rajapaksha, Acknowledgments 206
Nadeeshani Nanayakkara and Meththika Vithanage References 206

7.1 Introduction 167 9. Integrated CO2 sequestration,

7.2 Synthesis and properties of hydroxyapatite 168 wastewater treatment, and biofuel
7.2.1 Synthesis techniques 168 production by microalgae culturing:
7.2.2 Properties of hydroxyapatite 169 Needs and limitations 217
7.3 Hydroxyapatite as an adsorbent for
Khushboo Iqbal, Neha Sharma, Simran Takkar, Smriti Shukla,
wastewater treatment 170
Kartikeya Shukla, Ajit Varma and Arti Mishra
7.3.1 Common pollutants in wastewater 170
7.3.2 Removal of pollutants 174 9.1 Introduction 217
x Contents

9.2 Integrated carbon sequestration and its 10.5.6 Ozonation 252

sequestration technologies 219 10.5.7 Disinfection 252
9.2.1 Integrated approach in wastewater 10.6 Biotechnological approaches for removal
treatment 222 of contaminants from wastewater 252
9.2.2 Limitations of carbon sequestration 10.6.1 Bioremediation 254
technologies 225 10.6.2 Phytoremediation 255
9.2.3 Applications of integrated carbon 10.6.3 Mycoremediation 255
sequestration technologies 225 10.6.4 Phycoremediation 255
9.3 Microalgae-based biorefinery 226 10.6.5 Nanobiotechnology 256
9.3.1 Biorefinery products 227 10.7 Conclusions 256
9.4 Products obtained from biorefinery for References 258
biofuel industry 230
9.4.1 Bioethanol 230 11. Integrated biopolymer and bioenergy
9.4.2 Biodiesel 231 production from organic wastes: Recent
9.4.3 Biomethane 231
advances and future outlook 261
9.4.4 Biofertilizers 232
9.4.5 Biohydrogen 232 Anum Iqbal, Amani Al-Othman and Nasser M. Hamdan

9.5 Applications of microalgal biomass 233

11.1 Introduction 261
9.6 Limitations of algal biomass products 233
11.2 Structural and chemical characteristics
9.7 Conclusion 234
of biopolymer and bioenergy 263
Acknowledgments 234
11.3 Chemical insights into organic wastes 267
References 234
11.4 Traditional technologies for bioenergy
and biopolymer production through
10. Physicochemical–biotechnological organic wastes 269
approaches for removal of contaminants 11.4.1 Conventional incineration 269
from wastewater 241 11.4.2 Hydrothermal incineration and
Dilshad Begum Golgeri M, Syeda Ulfath Tazeen Kadri, oxidation 270
Satish Kumar Murari, Dummi Mahadevan Gurumurthy, 11.4.3 Pyrolysis 270
Muhammad Bilal, Ram Naresh Bharagava, Anyi Hu, 11.4.4 Liquefaction 270
Paul Olusegun Bankole, Luiz Fernando R. Ferreira and
11.4.5 Gasification 271
Sikandar I. Mulla
11.4.6 Transesterification 271
10.1 Introduction 242 11.4.7 Process intensification 272
10.2 Water pollution 243 11.4.8 Anaerobic digestion or
10.2.1 Causes and nature of contamination 243 biomethanation 272
10.3 Wastewater treatment - general scheme 245 11.5 Advanced biotechnology techniques
10.4 Physicochemical approaches for removal of (integrated systems) 272
contaminants from wastewater 247 11.6 Conclusion 275
10.4.1 Screening and use of grit chambers 247 References 276
10.4.2 Flotation 247
10.4.3 Sedimentation 248 12. Integrated production of
10.4.4 Centrifugal separation 248
10.4.5 Filtration 248
polyhydroxyalkonate (bioplastic) with
10.4.6 Reverse osmosis (RO) 249 municipal wastewater and sludge treatment
10.5 Chemical approach 249 for sustainable development 283
10.5.1 Neutralization 249 Mukesh Kumar, Inderpal Devgona, Ritu Bala, Abhishek Rana,
10.5.2 Precipitation 249 Manpreet Kaur Somal, Rohan Samir Kumar Sachan and
10.5.3 Flocculation 251 Arun Karnwal
10.5.4 Redox reactions 251
10.5.5 Adsorption with activated carbon 251 12.1 Introduction 283
 Contents xi

12.2 Enzymes, structure and properties of 14. Integrating forward osmosis into
polyhydroxyalkonate 285 microbial fuel cells for
12.3 Overview of different substrate for wastewater treatment 321
PHA production 287
Abdallah Alhajar, Muhammad Tawalbeh, Dana Arjomand,
12.4 Chemical environment and composition
Nooruddin Abdel Rahman, Hassan Khan and Amani Al-Othman
of wastewater sludge 291
12.5 Production of PHA using pure and mixed 14.1 Introduction 321
microbial cultures 292 14.1.1 Microbial fuel cell 322
12.6 Integration of polyhydroxyalkonate 14.1.2 Forward osmosis 324
production process with wastewater treatment 14.2 Membrane transport theory 325
plant 293 14.3 Osmotic microbial fuel cells 326
12.7 Growing impact and policies of PHA-based 14.3.1 Operational and manufactural
bioplastic in the world 296 observations 327
12.8 Conclusion 298 14.3.2 Applications 328
References 298 14.4 Challenges and obstacles 328
14.4.1 Reverse solute flux 329
14.4.2 Cost and efficiency 329
13. Wastewater treatment by oleaginous 14.4.3 Membranes 330
algae and biodiesel production: 14.5 Previous studies on OsMFCs 330
Prospects and challenges 303 14.6 Conclusions 332
Narasiman Nirmala, Shanmuganantham Selvanantham Dawn
References 332
and Jayaseelan Arun
15. Recent trends for treatment of
13.1 Introduction 303 environmental contaminants in wastewater:
13.2 Contaminants in industrial wastewater 305
An integrated valorization of
13.3 Microalgae and industrial wastewater 306
13.3.1 Microalgae and agro-industrial industrial wastewater 337
wastewater 307 Edwin Hualpa-Cutipa, Richard Andi Solórzano Acosta,
13.3.2 Microalgae and heavy metal Sheena Sangay-Tucto, Xiomara Gisela Mendoza Beingolea,
Gianfranco Talavera Gutierrez and Isabel Navarro Zabarburú
wastewater 307
13.3.3 Microalgae and textile dye 15.1 Introduction 337
wastewater 310 15.2 Physicochemical removal of pollutants
13.4 Prospects of microalgae for biofuel from wastewater generated by industries 338
production 310 15.2.1 Removal of adsorption 339
13.4.1 Advantages of utilizing microalgae 15.2.2 Removal by ion exchange 340
for biodiesel production 310 15.2.3 Removing by nanotechnology 342
13.4.2 Lipids from microalgae 311 15.2.4 Removal by electrocoagulation 342
13.4.3 Induction of neutral lipid production 311 15.2.5 Removal by membrane processes 344
13.4.4 Extraction of oil from microalgae 15.2.6 Removal by chemical precipitation 344
and its different techniques 311 15.2.7 Removal by magnetic extraction 347
13.5 Conversion of algal oil to biodiesel 313 15.2.8 Removal for biofiltration 347
13.5.1 Catalytic transesterification methods 314 15.3 Biotechnological removal of pollutants
13.6 Biofuels and bioproducts acquired from from wastewater generated by industries 348
biovolarization of algal biomass 315 15.3.1 Phytoremediation 348
13.6.1 Biodiesel 315 15.3.2 Bioaccumulation removal 348
13.6.2 Biomethane 316 15.3.3 Biomineralization removal 349
13.6.3 Bioethanol 316 15.3.4 Biotransformation removal 349
13.6.4 Biochar 316 15.3.5 Removal by bioadsorption 355
13.7 Conclusion 317 15.3.6 Bacteria and fungus degradation 355
References 317
xii Contents

15.4 Combined physicochemical-biotechnological 17.4 Challenges and limitations 391

strategies 356 17.5 Future scope 405
15.5 Drawbacks and future perspectives 358 17.6 Conclusion 406
References 359 References 407

16. Advancements in industrial 18. Nanostructured materials for

wastewater treatment by integrated water/wastewater remediation 413
membrane technologies 369 Junaid Munawar, Ehsan Ullah Rashid, Shahid Nawaz, Nisar Ali,
Vineet Kumar, Hafiz M.N. Iqbal and Muhammad Bilal
Sathya Udayakumar and Keerthi Praveen

16.1 Introduction 369 18.1 Introduction 413

16.2 Fundamentals of MBR 370 18.2 Wastewater and their sources 414
16.2.1 Membrane flux 370 18.3 Nanomaterials for water remediation
16.2.2 Membrane resistance 371 process 416
16.3 Hybrid MBR for high-strength wastewater 371 18.4 Carbon-based nanomaterials 417
16.4 MBR for tannery wastewater treatment 371 18.4.1 Graphene-based nanomaterials 417
16.5 MBR for textile wastewater treatment 373 18.4.2 Carbon nanotubes 419
16.5.1 Characterization of textile 18.5 Metal and metal oxides nanoparticles 420
wastewaters 374 18.5.1 Silver nanoparticles 420
16.5.2 Hybrid MBR for textile wastewater 18.5.2 Nano zerovalent Fe particles 421
treatment 374 18.5.3 Nano-TiO2 particles 422
16.6 MBR for pharmaceutical wastewater 376 18.5.4 Magnetic nanoparticles 423
16.7 Membrane fouling 377 18.6 Nanocomposite and nanofibers membrane 424
16.7.1 Biofouling by extracellular 18.6.1 Self-assembling membranes 426
polymeric substances (EPS) and 18.6.2 Clay-based nanoadsorbents 426
soluble microbial products (SMP) 378 18.7 Conclusion and future aspects 426
16.8 Strategies to reduce membrane fouling 378 References 427
16.8.1 Material configuration for fouling
19. Integrated technologies for
reduction 379
16.8.2 Integration of treatment system for wastewater treatment 433
fouling reduction 379 Simranjeet Singh, Dhriti Kapoor, Vaishali Dhaka, Savita Bhardwaj,
16.9 Conclusions 379 Praveen C. Ramamurthy and Joginder Singh

References 380
19.1 Introduction 433
17. Microbial electrochemical-based 19.2 Current situation of wastewater treatment
and management 435
constructed wetland technology for
19.3 New concepts and technologies for
wastewater treatment: Reality, challenges, wastewater treatment 437
and future prospects 383 19.3.1 Wastewater treatment using activated
Divyani Kumari, Achlesh Daverey and Kasturi Dutta carbon 437
19.3.2 Wastewater treatment using
17.1 Introduction 383 nanoparticles 439
17.2 Integration of BES with CW (CW-BES) 385 19.3.3 Carbon nanotubes and wastewater
17.2.1 Fundamentals of BES 385 cleansing 440
17.2.2 Advantages of integrating BES 19.3.4 Microbial fuel cells 442
with CW 387 19.4 Advanced integrated technologies for
17.2.3 Design of CW-BES systems and wastewater treatment 443
requirements 388 19.5 Potential benefits of integrated technologies
17.3 Wastewater treatment using CW-BES used in wastewater treatment 446
(lab-, pilot-, and full-scale studies) 389 19.6 Conclusion 449
 Contents xiii

Acknowledgements 449 22.2 Unscientific discharge of effluents:

References 449 A serious environmental issue 509
22.2.1 Composition of different
20. Integrated anaerobic-aerobic processes effluents 510
for treatment of high strength wastewater: 22.2.2 Probable solutions from water
Consolidated application, new trends, pollution 513
perspectives, and challenges 457 22.3 Potential role of microorganisms in
remediating wastewater 513
Malliga Perumal, Sivasankari Karikalacholan, Nirosha Parimannan,
Janci Arichandran, Keerthana Shanmuganathan, Ragavi Ravi, 22.3.1 Role of bacteria in treating
Sadhumathiya Jayapandiyan, Swathi Jayakumar and wastewater 514
Thilothi Mohandas 22.3.2 Role of microalgae in treating
waste water 515
20.1 Introduction 457 22.3.3 Microalgae-bacterial consortia in
20.2 Integrated anaerobic and aerobic treatment treating wastewater 517
of high strength wastewater 458 22.4 Alternative use of microalgae-bacteria
20.2.1 Consolidated application 458 consortia 522
20.2.2 New trends, perspectives, 22.4.1 Biohydrogen: An alternative
and challenges 472 bioenergy 523
20.3 Conclusion 477 22.4.2 Potential drawbacks in biohydrogen
Acknowledgements 478 production by microalgae-bacteria
References 478 consortia 526
21. Integrated biomedical waste 22.5 Comparative analysis of biohydrogen
over conventional fuels 526
degradation and detoxification 481 22.6 Future aspect of biohydrogen production
Nandini Singh, Ishita Shreshtha, Rishabh and Vinod Kumar Nigam from microalgae-bacteria consortia 527
Reference 527
21.1 Introduction 481
21.2 Sources of biomedical waste 482
21.2.1 Medical waste types 482
21.2.2 Biomedical waste segregation/sorting 484
23. Cyanobacteria mediated toxic metal
21.2.3 Detoxification of waste 485 removal as complementary and alternative
21.3 Disposal strategies 485 wastewater treatment strategy 533
21.4 Strategies and mechanism of degradation 489 Khalida Bloch and Sougata Ghosh
21.4.1 Thermochemical methods 489
21.4.2 Biochemical methods 492 23.1 Introduction 533
21.5 Constraints 497 23.2 Metal toxicity 534
21.6 Future scope 499 23.3 Cyanobacteria mediated metal removal 534
21.7 Some advanced approaches to treat 23.3.1 Antimony 534
medical waste 500 23.3.2 Arsenic 536
21.8 Conclusion and prospects 503 23.3.3 Cadmium 538
References 505 23.3.4 Chromium 540
23.3.5 Copper 542
22. Role of algal-bacterial association in 23.3.6 Lead 542
combined wastewater treatment and 23.3.7 Selenium 543
biohydrogen generation: An overview 23.4 Mechanism 545
on its challenges and future 509 23.5 Conclusions and future perspectives 545
References 545
Soumya Banerjee and Anoar A. Khan

22.1 Introduction 509 Index 549

 Contributors
Richard Andi Solórzano Acosta Escuela de In-
geniería Ambiental, Universidad César Vallejo,
Lima-Este., Perú
Abdallah Alhajar Department of Chemical En-
gineering, American University of Sharjah,
Sharjah, United Arab Emirates
Nisar Ali Key Laboratory for Palygorskite
Science and Applied Technology of Jiangsu
Province, National & Local Joint Engineering
Research Centre for Deep Utilization
Technology of Rock-salt Resource, Faculty
of Chemical Engineering, Huaiyin Institute of
Technology, Huai’an, China.
Dana Al-Muqbel Department of Chemical En-
gineering, American University of Sharjah,
Sharjah, United Arab Emirates
Mohammed Al-Murisi Department of Chemi-
cal Engineering, American University of Shar-
jah, Sharjah, United Arab Emirates
Amani Al-Othman Department of Chemical En-
gineering, American University of Sharjah,
Sharjah, United Arab Emirates
Dana Arjomand Department of Chemical Engi-
neering, American University of Sharjah, Shar-
jah, United Arab Emirates
Janci Arichandran Department of Biotechnol-
ogy, Bharathidasan University, Tiruchirappalli,
Tamil Nadu, India
Jayaseelan Arun Centre for Waste Management,
Sathyabama Institute of Science and Technol-
ogy, Chennai, Tamil Nadu, India
Manuel Javier Aybar Instituto Superior de In-
vestigaciones Biológicas (INSIBIO, CONICET-
Universidad Nacional de Tucumán), Tucumán,
Argentina; Instituto de Biología “Dr. Francisco
D. Barbieri”, Facultad de Bioquímica, Química
y Farmacia, Universidad Nacional de Tucumán,
Tucumán, Argentina
xv
Ritu Bala Department of Microbiology, School of
Bioengineering and Biosciences, Lovely Profes-
sional University, Phagwara, Punjab, India
Soumya Banerjee Department of Basic Science
and Humanities, Hooghly Engineering & Tech-
nology College, Chinsurah, West Bengal, India
Paul Olusegun Bankole Department of Pure
and Applied Botany, College of Biosciences,
Federal University of Agriculture, Abeokuta,
Ogun State, Nigeria
Xiomara Gisela Mendoza Beingolea Faculty of
Pharmacy and Biochemistry, Universidad Na-
cional Mayor de San Marcos, Lima, Perú
Ram Naresh Bharagava Department of Microbi-
ology (DM), School for Environmental Sciences
(SES), Babasaheb Bhimrao Ambedkar Univer-
sity (A Central University), Lucknow, Uttar
Pradesh, India
Savita Bhardwaj Department of Botany, School
of Bioengineering and Biosciences, Lovely Pro-
fessional University, Phagwara, Punjab, India
Amit Bhatnagar Department of Separation Sci-
ence, LUT School of Engineering Science, LUT
University, Mikkeli, Finland
Muhammad Bilal School of Life Science and
Food Engineering, Huaiyin Institute of Technol-
ogy, Huai’an, China
Jayanta Kumar Biswas Enviromicrobiology,
Ecotoxicology and Ecotechnology Research
Laboratory, Department of Ecological Studies,
University of Kalyani, Kalyani, Nadia,
West Bengal, India; International Centre for
Ecological Engineering, University of Kalyani,
Kalyani, West Bengal, India
Soma Biswas Energy and Environment Re-
search Laboratory, Department of Electrical En-
gineering, Dr. B. C. Roy Engineering College,
Durgapur, West Bengal, India
xvi Contributors
Khalida Bloch Department of Microbiology,
School of Science, RK University, Rajkot,
Gujarat, India
Himani Chandel EMBL-Environmental Micro-
biology and Biotechnology Laboratory, EERG-
Ecotoxicology and Environmental Remediation
Group, School of Biotechnology, Shoolini Uni-
versity of Biotechnology and Management Sci-
ences, Solan, Himachal Pradesh, India
Zhen Hong Chang Department of Chemical
Engineering and Process, Faculty of Engi-
neering and Built Environment, University
Kebangsaan Malaysia, UKM Bangi, Selangor
Darul Ehsan, Malaysia; Department of Chemi-
cal and Petroleum Engineering, Faculty of En-
gineering, Technology and Built Environment,
UCSI University, Kuala Lumpur, Malaysia
Akanksha Chauhan Environment and Biofuel
Research Lab, Hydro and Renewable Energy
Department, Indian Institute of Technology
(IIT) Roorkee, Roorkee, Uttarakhand,
India
Achlesh Daverey School of Environment and
Natural Sources, Doon University, Dehradun,
Uttarakhand, India
Shanmuganantham Selvanantham Dawn
Centre for Waste Management, Sathyabama
Institute of Science and Technology, Chennai,
Tamil Nadu, India; Centre of Excellence for
Energy Research, Sathyabama Institute of
Science and Technology, Chennai, Tamil Nadu,
India
Inderpal Devgon Department of Microbiology,
School of Bioengineering and Biosciences,
Lovely Professional University, Phagwara,
Punjab, India
Vaishali Dhaka Department of Microbiology,
Lovely Professional University, Phagwara, Pun-
jab, India
Govindaraj Divyapriya Department of Civil
and Environmental Engineering, Virginia Poly-
technic Institute and State University, Blacks-
burg, United States
Kasturi Dutta Department of Biotechnology and
Medical Engineering, National Institute of Tech-
nology Rourkela, Odisha, India
Pablo Marcelo Fernández Planta Piloto de Pro-
cesos Industriales Microbiológicos (PROIMI-
CONICET), Tucumán, Argentina; Universidad
Nacional de Catamarca, Catamarca, Argentina
Luiz Fernando R. Ferreira Waste and Effluent
Treatment Laboratory, Institute of Technol-
ogy and Research (ITP), Tiradentes University,
Farolândia, Aracaju, SE, Brazil
Lucía Inés Castellanos de Figueroa Planta Pi-
loto de Procesos Industriales Microbiológicos
(PROIMI-CONICET), Tucumán, Argentina
Sougata Ghosh Department of Microbiology,
School of Science, RK University, Rajkot, Gu-
jarat, India
Dilshad Begum Golgeri M Department of
Biochemistry, School of Applied Sciences,
REVA University, Bangalore, Karnataka, India;
Department of Biochemistry, Indian Academy
Degree College Autonomous, Bangalore,
Karnataka, India
Dummi Mahadevan Gurumurthy Department
of Biotechnology, GM Institute of Technology,
Davangere, Karnataka, India
Gianfranco Talavera Gutierrez Faculty of Phar-
macy and Biochemistry, Universidad Nacional
Mayor de San Marcos, Lima, Perú
Nasser M. Hamdan Department of Physics, Col-
lege of Arts and Sciences, American University
of Sharjah, United Arab Emirates
Oshadi Hettithanthri Ecosphere Resilience Re-
search Centre, Faculty of Applied Sciences, Uni-
versity of Sri Jayewardenepura, Nugegoda, Sri
Lanka
Kah Chun Ho Faculty of Engineering, Built En-
vironment, and Information Technology, SEGi
University, Kota Damansara, Malaysia
Anyi Hu CAS Key Laboratory of Urban Pollu-
tant Conversion, Institute of Urban Environ-
ment Chinese Academy of Sciences, Xiamen,
China
Edwin Hualpa-Cutipa Faculty of Pharmacy and
Biochemistry, Biotechnology and Omics in Life
Sciences Research Group, Universidad Na-
cional Mayor de San Marcos, Lima, Perú;
Universidad César Vallejo
 Contributors
Anum Iqbal Material Sciences and Engineer-
ing Program, American University of Sharjah,
United Arab Emirates
Hafiz M.N. Iqbal Tecnologico de Monterrey,
School of Engineering and Sciences, Monterrey,
Mexico
Khushboo Iqbal Amity Institute of Microbial
Technology, Amity University, Noida, Uttar
Pradesh, India
Swathi Jayakumar Department of Biotechnol-
ogy, Bharathidasan University, Tiruchirappalli,
Tamil Nadu, India
Sadhumathiya Jayapandiyan Department
of Biotechnology, Bharathidasan University,
Tiruchirappalli, Tamil Nadu, India
Mahmood Gheni Jebur Ralph E Martin De-
partment of Chemical Engineering, University
of Arkansas, Fayetteville, AR, USA; Depart-
ment of Chemical Engineering, Tikrit Univer-
sity, Tikrit, Salah Al-din, Iraq
Syeda Ulfath Tazeen Kadri Department of Bio-
chemistry, School of Applied Sciences, REVA
University, Bangalore, Karnataka, India
Dhriti Kapoor Department of Botany, School
of Bioengineering and Biosciences, Lovely
Professional University, Phagwara, Punjab,
India
Ansaf V. Karim Environmental Science and En-
gineering Department, Indian Institute of Tech-
nology Bombay, Powai, Mumbai, India
Arun Karnwal Department of Microbiology,
School of Bioengineering and Biosciences,
Lovely Professional University, Phagwara,
Punjab, India
Sivasankari Karikalacholan Department of Ma-
rine Biotechnology, Bharathidasan University,
Tiruchirappalli, Tamil Nadu, India
Keerthi Praveen Department of Chemistry,
Anna University, Chennai, Tamil Nadu, India
Anoar A. Khan Chemical Engineering
Department, Vignan’s Foundation for Science,
Technology & Research, Vadlamudi, Guntur,
Andhra Pradesh, India
Hassan Khan Department of Chemical Engi-
neering, American University of Sharjah, Shar-
jah, United Arab Emirates
xvii
Pabasari Arundathi Koliyabandara Ecosphere
Resilience Research Centre, Faculty of Applied
Sciences, University of Sri Jayewardenepura,
Nugegoda, Sri Lanka; Faculty of Technology,
University of Sri Jayewardenepura, Pitipana, Sri
Lanka
Mukesh Kumar Department of Microbiology,
School of Bioengineering and Biosciences,
Lovely Professional University, Phagwara,
Punjab, India
Navneet Kumar EMBL-Environmental Micro-
biology and Biotechnology Laboratory, EERG-
Ecotoxicology and Environmental Remediation
Group, School of Biotechnology, Shoolini
University of Biotechnology and Management
Sciences, Solan, Himachal Pradesh,
India
Vineet Kumar Waste Re-processing Division,
CSIR-National Environmental Engineering Re-
search Institute (CSIR-NEERI), Nehru Marg,
Nagpur, Maharashtra-440020, India
Divyani Kumari Department of Biotechnology
and Medical Engineering, National Institute of
Technology Rourkela, Odisha, India
Débora Daniela Maza Instituto Superior de In-
vestigaciones Biológicas (INSIBIO, CONICET-
Universidad Nacional de Tucumán), Tucumán,
Argentina
Arti Mishra Amity Institute of Microbial
Technology, Amity University, Noida, Uttar
Pradesh, India
Thilothi Mohandas Department of Biotechnol-
ogy, Bharathidasan University, Tiruchirappalli,
Tamil Nadu, India
Monojit Mondal Enviromicrobiology, Ecotoxi-
cology and Ecotechnology Research Labora-
tory, Department of Ecological Studies, Univer-
sity of Kalyani, Kalyani, Nadia, West Bengal,
India
Sikandar I. Mulla Department of Biochemistry,
School of Applied Sciences, REVA University,
Bangalore, Karnataka, India
Junaid Munawar College of Chemistry, Beijing
University of Chemical Technology, PR China
xviii Contributors
Satish Kumar Murari Department of Biochem-
istry, School of Applied Sciences, REVA Univer-
sity, Bangalore, Karnataka, India
Sibiraj Murugesan EMBL-Environmental
Microbiology and Biotechnology Laboratory,
EERG-Ecotoxicology and Environmental
Remediation Group, School of Biotechnology,
Shoolini University of Biotechnology and
Management Sciences, Solan, Himachal
Pradesh, India
Nadeeshani Nanayakkara Department of Civil
Engineering, University of Peradeniya, Per-
adeniya, Sri Lanka
Shahid Nawaz Department of Chemistry, The
University of Lahore, Lahore, Pakistan
Puthiya Veetil Nidheesh Environmental Impact
and Sustainability Division, CSIR-National En-
vironmental Engineering Research Institute,
Nagpur, Maharashtra, India
Vinod Kumar Nigam Department of Bioengi-
neering and Biotechnology, Birla Institute of
Technology, Mesra, Ranchi
Narasiman Nirmala Centre for Waste Manage-
ment, Sathyabama Institute of Science and Tech-
nology, Chennai, Tamil Nadu, India
Nirosha Parimannan Department of Marine
Biotechnology, Bharathidasan University,
Tiruchirappalli, Tamil Nadu, India
Lakshmi Pisharody The Zuckerberg Institute of
Water Research, Ben-Gurion University, Beer-
sheba, Israel
Malliga Perumal Department of Marine
Biotechnology, Bharathidasan University,
Tiruchirappalli, Tamil Nadu, India
Sanjeev Kumar Prajapati Environment and Bio-
fuel Research Lab, Hydro and Renewable En-
ergy Department, Indian Institute of Tech-
nology (IIT) Roorkee, Roorkee, Uttarakhand,
India
Nooruddin Abdel Rahman Department of
Chemical Engineering, American University of
Sharjah, Sharjah, United Arab Emirates
Anushka Upamali Rajapaksha Ecosphere
Resilience Research Centre, Faculty of Applied
Sciences, University of Sri Jayewardenepura,
Nugegoda, Sri Lanka; Instrument Center,
Faculty of Applied Sciences, University
of Sri Jayewardenepura, Nugegoda,
Sri Lanka
Praveen C. Ramamurthy Interdisciplinary Cen-
tre for Water Research (ICWaR), Indian Institute
of Sciences, Bangalore, India
Abhishek Rana Jindal Global Law School, O.P.
Jindal Global University, Sonipat, Haryana, In-
dia
Ehsan Ullah Rashid Department of Chemistry,
University of Agriculture Faisalabad, Faisal-
abad, Pakistan
Anushka Rathnayake Ecosphere Resilience Re-
search Centre, Faculty of Applied Sciences, Uni-
versity of Sri Jayewardenepura, Nugegoda, Sri
Lanka; Institute of Chemistry Ceylon, Raja-
giriya, Sri Lanka
Ragavi Ravi Department of Biotechnology,
Bharathidasan University, Tiruchirappalli,
Tamil Nadu, India
Rishabh Motilal Nehru Medical College, Praya-
graj
Rohan Samir Kumar Sachan Department of Mi-
crobiology, School of Bioengineering and Bio-
sciences, Lovely Professional University, Phag-
wara, Punjab, India
Sheena Sangay-Tucto Centro de Investigación
y Tecnología del Agua (CITA), Departamento
de Ingeniería Ambiental, Universidad de Inge-
niería y Tecnología (UTEC), Lima, Perú
Gaurav Saxena EMBL-Environmental Microbi-
ology and Biotechnology Laboratory, EERG-
Ecotoxicology and Environmental Remediation
Group, School of Biotechnology, Shoolini Uni-
versity of Biotechnology and Management Sci-
ences, Solan, Himachal Pradesh, India
Keerthana Shanmuganathan Department of
Biotechnology, Bharathidasan University,
Tiruchirappalli, Tamil Nadu, India
Geetansh Sharma EMBL-Environmental
Microbiology and Biotechnology Laboratory,
EERG-Ecotoxicology and Environmental
Remediation Group, School of Biotechnology,
Shoolini University of Biotechnology and
 Contributors
Management Sciences, Solan, Himachal
Pradesh, India
Neha Sharma Amity Institute of Microbial
Technology, Amity University, Noida, Uttar
Pradesh, India
Ishita Shreshtha Department of Bioengineering
and Biotechnology, Birla Institute of Technol-
ogy, Mesra, Ranchi
Kartikeya Shukla Amity Institute of Environ-
mental Sciences, Amity University, Noida, India
Smriti Shukla Amity Institute of Environmen-
tal Toxicology, Safety and Management, Amity
University, Noida, Uttar Pradesh, India
Joginder Singh Department of Microbiology,
Lovely Professional University, Phagwara, Pun-
jab, India
Nandini Singh Department of Bioengineering
and Biotechnology, Birla Institute of Technol-
ogy, Mesra, Ranchi
Simranjeet Singh Interdisciplinary Centre for
Water Research (ICWaR), Indian Institute of Sci-
ences, Bangalore, India
Manpreet Kaur Somal Department of Biotech-
nology, School of Bioengineering and Bio-
sciences, Lovely Professional University, Phag-
wara, Punjab, India
Kirti Shyam EMBL-Environmental Microbiol-
ogy and Biotechnology Laboratory, EERG-
Ecotoxicology and Environmental Remediation
Group, School of Biotechnology, Shoolini Uni-
versity of Biotechnology and Management Sci-
ences, Solan, Himachal Pradesh, India
Simran Takkar Amity Institute of Microbial
Technology, Amity University, Noida, Uttar
Pradesh, India
Muhammad Tawalbeh Department of Sus-
tainable and Renewable Energy Engineering,
University of Sharjah, Sharjah, United Arab
Emirates
Yeit Haan Teow Department of Chemical
Engineering and Process, Faculty of
Engineering and Built Environment, University
Kebangsaan Malaysia, UKM Bangi, Selangor
xix
Darul Ehsan, Malaysia; Research Centre for
Sustainable Process Technology, Faculty of
Engineering and Built Environment, University
Kebangsaan Malaysia, UKM Bangi, Selangor
Darul Ehsan, Malaysia
Saurabh Thakur EMBL-Environmental Micro-
biology and Biotechnology Laboratory, EERG-
Ecotoxicology and Environmental Remediation
Group, School of Biotechnology, Shoolini Uni-
versity of Biotechnology and Management Sci-
ences, Solan, Himachal Pradesh, India
Sathya Udayakumar Environmental Engineer-
ing Department, CSIR-Central Leather Research
Institute, Chennai, Tamil Nadu, India
Ajit Varma Amity Institute of Microbial Technol-
ogy, Amity University, Noida, Uttar Pradesh,
India
Silvana Carolina Viñarta Planta Piloto de Pro-
cesos Industriales Microbiológicos (PROIMI-
CONICET), Tucumán, Argentina; Universidad
Nacional de Catamarca, Catamarca, Argentina
Meththika Vithanage Ecosphere Resilience Re-
search Centre, Faculty of Applied Sciences, Uni-
versity of Sri Jayewardenepura, Nugegoda, Sri
Lanka; Molecular Microbiology and Human
Diseases Group, National Institute of Funda-
mental Studies, Kandy, Sri Lanka
Sumith Ranil Wickramasinghe Department of
Chemical Engineering and Process, Faculty of
Engineering and Built Environment, University
Kebangsaan Malaysia, UKM Bangi, Selangor
Darul Ehsan, Malaysia; Ralph E Martin Depart-
ment of Chemical Engineering, University of
Arkansas, Fayetteville, AR, USA
Manu Yadav EMBL-Environmental Microbi-
ology and Biotechnology Laboratory, EERG-
Ecotoxicology and Environmental Remediation
Group, School of Biotechnology, Shoolini
University of Biotechnology and Management
Sciences, Solan, Himachal Pradesh,
India
Isabel Navarro Zabarburú Faculty of Pharmacy
and Biochemistry, Universidad Nacional Mayor
de San Marcos, Lima, Perú
 About the editors

Dr. Vineet Kumar is currently working as a Senior Project

Associate in the Waste Re-processing Division at CSIR-National
Environmental Engineering Research Institute (NEERI), Nagpur,
Maharashtra, India. Before his joining, he worked as Assistant
Professor (Ad-hoc) in the Department of Botany at Guru Ghasidas
Vishwavidyalaya, Bilaspur, India. He worked as Assistant Profes-
sor and Academic Coordinator at Vinayak Vidyapeeth, Meerut,
Uttar Pradesh, India. Dr. Kumar received his M.Sc. and M.Phil.
degree in Microbiology from Ch. Charan Singh University, Meerut,
India. He earned his Ph.D. in Environmental Microbiology from
Babasaheb Bhimaro Ambedkar (A Central) University, Lucknow,
India and later worked at the Dr. Shakuntala Misra National Reha-
bilitation University, Lucknow, India as a Guest Faculty where he taught courses in general
microbiology, microbial genetics, molecular biology, and environmental microbiology to stu-
dents of post graduate-level. He was awarded a Rajiv Gandhi National Fellowship by the
University Grants Commission, India to support his doctoral work on “Distillery Wastew-
ater Treatment” in 2013. His research interests include bioremediation, phytoremediation,
metagenomics, wastewater treatment, environmental monitoring, and bioenergy and biofuel
production. Currently, his research mainly focuses on the development of integrated and
sustainable methods that can help in minimizing or eliminating hazardous substances in the
environment for sustainable development. He is the author of numerous research/review
articles published in international peer-reviewed journals from Springer Nature, Frontiers,
and Elsevier on the different aspects of bioremediation, phytoremediation, and metagenomics
of industrial waste polluted sites. In addition, he has published 15 Books on different aspects
of phytoremediation and bioremediation of wastewater or wastewater pollutants from CRC
Press (Taylor & Francis Group), and Elsevier Inc., USA. Dr. Kumar has been serving as a
guest editor and reviewer in many prestigious International Journals, including Frontiers
in Microbiology, Environmental Research, Chemosphere, Journal of Basic Microbiology; In-
ternational Journal of Environmental Science and Technology; CLEAN-Soil, Air, Water etc.
He is an active member of numerous scientific societies and has served the editorial board
of the journal Current Research in Wastewater Management, Biotechnology and Genetic
Engineering Reviews, and SN Applied Sciences. As part of his interest in teaching biology,
he is founder of the Society for Green Environment, India (website: www.sgeindia.org). He
can be reached at drvineet.micro@gmail.com; vineet.way18@gmail.com.

xxi
xxii About the editors

Dr. Manish Kumar is currently working as a Project Scientist at En-

vironmental Biotechnology and Genomic Division (EBGD), Council
of Scientific and Industrial Research, National Environmental En-
gineering Research Institute (CSIR–NEERI), Nagpur, Maharashtra,
India. Dr. Kumar did his postdoctoral research from Department
of Civil and Environmental Engineering (CEE), The Hong Kong
Polytechnic University, Hong Kong, China and Ph.D. from School of
Environmental Sciences, Jawaharlal Nehru University, New Delhi,
India. Dr. Kumar working area belongs to bioremediation, bio-
valorization, bioenergy, and detoxification of natural and organic
compounds, with major emphasis on waste biorefinery and circular
economy. He worked for Department of Science and Technology, Government of India sponsor
project and Department of Biotechnology (DBT), Government of India sponsored project.
He also worked for international collaborative project entitle “Indo-US Advanced Bioenergy
Consortium (IUABC): Second Generation Biofuels.” In 2018, he worked as Visiting Researcher
at École polytechnique fédérale de Lausanne (EPFL) Switzerland, Bioenergy and Energy
Planning Research Group (BPE). He has published more than 30 research and review papers
in peer review journals, 5 book chapters, and also applied for one patent. He has more than
850 Google citations with 17 h-index.
 Preface
These days, rising industrial, man-
ufacturing, and agricultural activities,
imposing huge demand of fresh water
and simultaneously producing significant
amount of wastewater. The generation
of wastewater imposes several grave
environmental issues related to its
treatments, reuse, and recycling. Due to
rising demands of new and emerging
products simultaneously imposing pressure
on industries to fulfill the demands which
leads to generation of emerging and
recalcitrant contaminants and further
their amalgamation in wastewater stream.
Traditional wastewater treatments methods
are inadequate to remove these emerging
pollutants, further worsening the issues
related to potable water globally. Henceforth,
there is an awful demand to upgrade the
existing wastewater treatment technologies
or to developed new technologies to
lessen the impacts of wastewater on the
environment and living being health.
Although wastewater treatment and
resource recovery methods have been widely
expanded by the researchers and industries
in present decades, still their large-scale
execution in treatments and recovery of
resources from wastewater is insignificant
due to several technical and no-technical
issues. Wastewater treatments technologies
and their management significant plays
a role in developing a sustainable urban
society. Conventionally, the main aim of
wastewater management and treatment
is to guard downstream consumers
from health-related issues. However,
these days, protecting the environments
xxiii
and prevention the surface and ground
water contamination from wastewater
containing extra nutrients loads, turn out
to be an additional objective. Subsequently,
technologies for removal of phosphorous
and nitrogen have been deployed recently
in wastewater treatment plants (WWTPs).
In current scenario, the most extensively
applied wastewater treatment and resource
recovery technology are the conventional
activated sludge method. Even though this
method is successful enough in maintaining
the quality of wastewater in view of its
legal discharge quality guideline, still
this process is ineffective in recovery of
resources, economics, and their high energy
intensiveness and environmental footprint.
The need for achieving the sustainability
as well as efficient usage of available
resources, existing wastewater treatment
technologies have provided a paradigm shift
inside the scientific minds with affection to
solution of wastewater. The issue now
recommends a change from removal of
contaminant from wastewater stream to
recovery of value added products, therefore,
wastewater could be realized as a feedstock
somewhat than an environmental waste.
It appears expected that we have to have
advance a new technology if we are willing
to cope up with rising population and
increasing living standards, which are
propelling our utilization of naturally
available resources toward boundaries
beyond environmental sustainability. In
spite of regular scientific outcome over
an extended time scale on technological
resolutions to create a better circular
xxiv
economy model related to treatment and
resource recovery from wastewater stream,
their execution at large-scale is infancy
and challenging. The execution of resource
recovery operation can be tedious due to
altering the existing technologies incurs extra
costs, generates operational interferences,
and utilizes additional resources. Due
to rising figures of existing resource
recovery approaches, WWT technologies
and their design are no more a manageable
technical issue, but a multifaceted topic that
needs a cohesive strategy to take effective
resolutions. Ambiguities related to which
approaches are most suitable and in what
way integrate them is still challenging. Along
with technical ambiguities that are effective
for several evolving resource recovery
approaches, numerous nontechnological
stumbling block could hamper the effective
execution of such approaches into treatment
of wastewater and recovery of resources.
Specifically, the market capacity and
competition for recovered resources from
wastewater stream present ambiguities. The
wastewater treatment sector has previously
been out of sorts equipment to address issues
related to conventional engineering-centered
room. Institutional compartmentalization
which adversely hampers integrated
water-resource recovery and management
strategy, must be improved so as to make
advancement in emerging resource recovery-
oriented management and treatment of
wastewater.
Therefore, the current book, entitled “Inte-
grated Environmental Technologies for Wastewa-
ter Treatment and Sustainable Development” dis-
cussed the strategies, implementation, cur-
rent finding and progress in treatment of
wastewater and recovery of resources based
on the circular economy model, which might
be helpful in achieving the goal of sus-
tainable environments. These context spe-
cific aspects have been covered with in
Preface
23 chapters contributed by leading researches
and scientists from all over the world having
expertise in wastewater treatment and bio-
valorization. It is well known that wastew-
ater treatment and resource recovery from
waste stream is a multidisciplinary tech-
nique where microbiologists, biotechnolo-
gists, biochemists, soil scientists, environ-
mental scientist, and etc. work jointly to
advance and successfully execute operation
to achieve the environmental sustainability.
Henceforth, in this book, many appropriate
subjects have been underwritten by special-
ists from various backgrounds, universities,
colleges, institutions, research and develop-
ment laboratories and industries, who per-
form basic, applied and engineering research
in the novel field of wastewater treatment
and resource recovery from waste streams
globally. This book covered, various issues
related to fundamental and cutting-edge in-
formation associated with wastewater treat-
ment and resource recovery for sustainable
environment, including Integration of Photo-
catalytic and Biological Processes for Treat-
ment of Complex Effluent: Recent Devel-
opments, Trends, and Advances; Anaerobic
Ammonium Oxidation (ANAMMOX) Tech-
nology for Nitrogen Removal from Wastew-
ater: Recent Advances and Challenges; Inno-
vative Integrated Treatment Approaches for
Recycling and Re-Use of Industrial and Mu-
nicipal Wastewater; Integrated Production of
Biodiesel and Industrial Wastewater Treat-
ment by Culturing Oleaginous Microorgan-
isms; Nature-inspired Ecotechnological Ap-
proaches Towards Recycling and Recovery
of Resources from Wastewater; Integrated
Microbial Desalination Cell and Microbial
Electrolysis Cell for Wastewater Treatment;
Hydroxyapatite for environmental remedi-
ation of water/wastewater; Algae Coupled
Constructed Wetland System for Wastew-
ater Treatment; Integrated Carbon Dioxide
Sequestration, Wastewater Treatment, and
 Preface
Biofuel Production by Microalgae Culturing:
Needs and Limitations; Physicochemical–
Biotechnological Approaches for Removal of
Contaminants from Wastewater; Integrated
Biopolymer and Bioenergy Production from
Organic Waste: Recent Advances and Fu-
ture Outlook; Integrated Production of Poly-
hydroxyalkonate (Bioplastic) with Munici-
pal Wastewater and Sludge Treatment for
Sustainable Development; Wastewater Treat-
ment by Oleaginous Algae and Biodiesel
Production: Prospects and Challenges; In-
tegrating Forward Osmosis into Microbial
Fuel Cells for Wastewater Treatment; Re-
cent Trends for Treatment of Environmental
Contaminants in Wastewater: An Integrated
Valorization of Industrial Wastewater; Ad-
vancements in Industrial Wastewater Treat-
ment by Integrated Membrane Technolo-
gies; Microbial Electrochemical Based Con-
structed Wetlands Technologies for Wastew-
ater Treatment: Reality, Challenges and Fu-
ture Prospects; Nanostructured Materials for
Water/Wastewater Remediation; Integrated
Technologies for Wastewater Treatment; Inte-
grated anaerobic-aerobic processes for treat-
ment of high strength wastewater: con-
solidated application, new trends, perspec-
tive and challenges; Integrated Biodegrada-
tion and Detoxification of Medical Waste;
Integrated Treatment of Industrial Efflu-
ents by Chemical Coagulation and Ozona-
xxv
tion, Cyanobacteria mediated toxic metal
removal from wastewater. All contributed
chapters in this book are understandable and
comprehensive discussed, with appropriate
photographical and graphical representation
to make the information uncomplicated and
deliver additional help and support in under-
standing the processes. The key goal of this
book is to provide in-depth knowledge about
wastewater treatments technologies and re-
covery of greener value-added products from
waste so as to uphold environmental sus-
tainability. We are hoping this book also
provides inordinate value to researchers, aca-
demicians, scientists, environmentalists, en-
trepreneurs, environmental engineers, leg-
islators, governing experts, dumping site
managers, and students belongs to various
disciplines and level such as bachelor, master,
doctoral along with other passionate persons
who are enthusiastically devoted to protect-
ing the environment for sustainability. We
have faith in that the various technologies
and approaches discussed in this book, im-
itate the key drifts of research work and
progress for the upcoming years.
Vineet Kumar
Nagpur, India
Manish Kumar
Nagpur, India
 Acknowledgments
We strongly believe that the successful
completion of this compendium of new
knowledge is possible because of the bless-
ings of “Almighty God.”
In this endeavor, we, the editors were not
alone, but assisted by many people. First, we,
the editors, would like to acknowledge all the
contributors who responded to our request
and contributed their chapters enthusiasti-
cally, containing the latest information on the
relevant aspects make this primer a reality.
Dr. Vineet Kumar expresses his sincere
thanks to Dr. Sunil Kumar, Senior Principal
Scientist and Head at Waste Re-processing
Division, CSIR-National Environmental En-
gineering Research Institute (CSIR-NEERI),
Nagpur, Maharashtra, India for his kind and
moral support and for providing a fantas-
tic facility in his laboratory to complete this
task.
Dr. Vineet Kumar is highly indebted to
Prof. V.K. Garg (Professor and Dean in the
School of Environment and Earth Sciences
at Central University of Punjab, Punjab), Dr.
V.P. Sharma (Chief Scientist, CSIR-Indian In-
stitute of Toxicology Research, Uttar Pradesh,
India), Dr. Sunil Kumar (Senior Principal Sci-
entist and Head in the Water Re-processing
Division, CSIR-National Environmental En-
gineering Research Institute, India), Dr. Lal
Singh (Senior Scientist CSIR-National En-
vironmental Engineering Research Institute,
India), who took the time to critically re-
view over individual manuscript of this
book. His useful comments have been grate-
fully received which improved the book
manuscripts.
xxvii
We are gratefully acknowledging the
constructive comments on submitted
manuscripts by anonymous reviewers.
We also record our the warmest appreci-
ation to all those who have participated and
helped in compiling this knowledgeable vol-
ume, more particularly Ms. Sakshi Agrawal,
Ph.D. Scholar in the Department of Botany
at Guru Ghasidas Vishwavidyalaya (A Cen-
tral University), Bilaspur, Chhattisgarh, In-
dia, who helped us in editing and compila-
tion of the manuscripts till submission to ed-
itorial project manager. Many thanks are due
to our staff, students and teachers (past and
present), colleagues, and friends who have
all contributed in small and big ways to this
effort.
We would also like to thank Elsevier for
giving us the opportunity to accomplish the
project and share the knowledge with the
scientific and academic fraternity. I am par-
ticularly indebted to Dr. Marinakis Kostas,
Executive Editor, for her motivation, trust, and
unconditional support till his retirement at
Elsevier who are simply the best. Thanks also
goes to Dr. Susan Dennis, Executive Editor at
Elsevier, who join this project in the middle,
for her constructive criticism and sound ad-
vice.
Special recognition and sincere apprecia-
tion are due to Dr. Judith Clarisse Punzalan
in his/her role as Editorial Project Manager
at Elsevier for ensuring smooth production
of this book, without his prodding, this book
would never have been completed.
We are also deeply indebted to the many
publishing professionals whose consistent
xxviii Acknowledgments
encouragement, hard work, and careful at-
tention to detail contributed much to the clar-
ity of both the text and the art. The elegant
design of the book’s cover page is due to the
efforts of the Mark Rogers, designer at Else-
vier, whose talents are evident. Thanks are
also due to Bharatwaj Varatharajan, Project
Manager at Elsevier who and his team skill-
fully laid out the pages for each chapter,
reviewed the material, and timely sent the
proof to authors.
Last but not the least, the editors would
like to acknowledge their family members,
their inspiration, endurance, and moral sup-
port during this long journey. Any success
that we have achieved or will achieve in
the future would not be possible without
the love and moral support of our beloved
families.
We should be pleased to receive any com-
ments on the content and style of Inte-
grated Environmental Technologies for Wastew-
ater Treatment and Sustainable Development
from students, professionals, environmental-
ist and policy makers, all of which will be
given serious consideration for inclusion in
any further editions.
Vineet Kumar
Nagpur, India
Manish Kumar
Nagpur, India
 C H A P T E R

1
Integration of photocatalytic and
biological processes for treatment
of complex effluent: Recent
developments, trends, and
advances
Govindaraj Divyapriya a, Lakshmi Pisharody b,
Ansaf V. Karim c and Puthiya Veetil Nidheesh d
a
Department of Civil and Environmental Engineering, Virginia Polytechnic Institute
and State University, Blacksburg, United States b The Zuckerberg Institute of Water
Research, Ben-Gurion University, Beersheba, Israel c Environmental Science and
Engineering Department, Indian Institute of Technology Bombay, Powai, Mumbai,
India d Environmental Impact and Sustainability Division, CSIR-National
Environmental Engineering Research Institute, Nagpur, Maharashtra, India

1.1 Introduction
The occurrence of organic pollutants in aquatic as well as nonaquatic environments due
to its potential for adverse health effects in human beings is a major cause of concern all
around the world. Rapid industrialization results in generating complex wastewater effluents
from different industries such as textiles, pharmaceutical, food processing, paper and pulp
etc. contribute majorly to the environmental pollution with a range of micropollutants that
are essentially organic in nature (Aziz et al., 2016). Moreover, these micropollutants have been
known to be potent carcinogens and toxic to human and aquatic life. Apart from the presence
of complex organic compounds, these industrial effluents are rich in nitrogen, phosphorous,
sulfur, color, and pathogens (Aziz et al., 2016). Hence, it is important to prevent its discharge

Integrated Environmental Technologies for Wastewater Treatment and 1 Copyright 

c 2022 Elsevier Inc. All rights reserved.
Sustainable Development
DOI: https://doi.org/10.1016/B978-0-323-91180-1.00024-7
2 1. Integration of photocatalytic and biological processes for treatment of complex effluent

into the environment by employing suitable treatment options and the quality of the treated
water should meet the discharge standards (Yang et al., 2017).
The refractory nature of organic compounds usually hinders their complete removal using
a single wastewater treatment process and the selection of treatment measure relies on the
inherent characteristics of the wastewater (Bahri et al., 2018). The conventional wastewater
treatment processes, including adsorption, sedimentation flocculation, filtration, etc., are
preferred to remove chemical oxygen demand (COD), turbidity, color, and suspended solids
leaving behind the waste sludge for further treatment. The biological processes are the least
expensive and most environmentally compatible process which uses the metabolic activities of
microbes, such as bacteria, fungi, algae, etc., that can oxidize or reduce organic contaminants
present in wastewater by using it as their carbon source (Ayed et al., 2017). However, due to
the recalcitrant nature of the wastewater the biological processes are inhibited due to enhanced
biotoxicity of the pollutants in the matrix. For instance, the requirement of a larger volume of
the biological systems with a large amount of sludge in the case of activated sludge process
to deal with higher COD loads increases the economic viability of the process and limits its
practical application (Bahri et al., 2018). Further, the toxicity of the variable organic compounds
can also prevent the activity of microbes and hinders the biodegradation process (Sharma and
Philip, 2016).
Advanced oxidation processes (AOPs) such as ozonation, sonolytic oxidation, photocatal-
ysis, and catalytic oxidation can be effectively used for the removal of organic compounds.
These technologies often lead to the complete mineralization of organic compounds. Among
them, the photocatalytic process which produces reactive oxygen species under irradiation in
the presence of a homogenous/heterogeneous catalyst is highly efficient for treating complex
effluents. They have proven to treat various complex wastewaters including textile, pharma-
ceutical, petrochemical and refinery, pesticides, etc. since they could potentially mineralize
the recalcitrant compounds (Bahri et al., 2018; Oller et al., 2011; Paździor et al., 2019). The
cost associated with various AOPs has been previously compared and in most cases UV-
based photocatalysis systems are the most expensive (Saritha et al., 2007). Also, the field scale
applications dealing with a large volume of wastewater makes these methods technically
difficult and appears economically unfavorable. Undoubtedly, AOPs have been applied on
field scale, however, practical applications are limited as the critical understanding of kinetic
reactions in complex environmental matrices is still lacking. Thus, combination treatment
mechanisms could be economical as well as efficient with respect to removal rate (Capodaglio,
2020).
Industrial effluents may contain organic compounds which are not readily biodegradable,
their nature may vary with their source (Shi et al., 2018). Pertaining the inherent characteristics
of the wastewater and their concentration, the treatment cost, a two stage chemical/biological
treatment could be an effective treatment route. In this regard, considering the environmental
compatibility, coupling of AOPs with the biological process for wastewater treatment is
more efficient and as it can reduce the concentration of compounds below the discharge
standards (Vidal et al., 2019). Advanced oxidation processes have the potential to improve the
biodegradability of wastewater containing higher COD concentration (Zhang et al., 2019). Hy-
brid process are promising treatment options to achieve complete removal of micropollutants
present in complex effluents with reduced cost of treatment (Aziz et al., 2016; Grandclément
et al., 2017; Moreira et al., 2015). In this regard, the combination of photocatalysis with the
 1.2 Biological treatment of organic contaminants 3

biological process could be a practical approach which could reduce the hazardous nature
of wastewater by oxidizing the organic compound present in complex effluent (Nidheesh
et al., 2021; Paździor et al., 2019). The photocatalysis process can be integrated with the
biological process either as pretreatment, post-treatment or as a multistep process to achieve
complete degradation of POPs present in complex effluents. This chapter provides a basic
mechanism of the biological and photocatalysis process and the need for their integration for
wastewater treatment. Further, the chapter also discusses the various approaches of integra-
tion of photocatalysis with biological process, mineralization potential and toxicity reduction.
Finally, the chapter reviews the available pilot-scale studies of process integration followed by
conclusion.

1.2 Biological treatment of organic contaminants

The micropollutants were treated using a variety of biological processes. Also, various
species of bacteria and fungi have been reported to be capable of degradation of the micropol-
lutants in the environment. Microbial degradation typically involves the catabolic activity of
the microorganisms, wherein the micropollutant acts as a growth substrate (Tran et al., 2013).
The sensitivity of microorganisms to the organic compound due to the diverse characteristics
of the wastewater can also effect on the degradation efficiency of processes. Major parameters
governing the microbial growth on micropollutants are temperature, pH, doubling time, light
requirement, and agitation (Cirja et al., 2008). Usually wastewater can be treated using aerobic
or anaerobic treatment process. Both systems use wastewaters from different pollutant sources
in more sophisticated and efficient bioreactors with activated sludge. The biological treatment
methods typically employed for the degradation of organic pollutants include conventional
treatment technologies, such as, activated sludge process (ASP), trickling and packed bed
systems. Several alternative and innovative biological processes are available for the removal
persistent organic pollutants which are more efficient than the conventional processes. Various
advanced biological treatment methods are also employed these days, that is, bioreactors
based with membranes or two-phase partitioning, or immobilized microorganisms (Kanaujiya
et al., 2019). Some of the popular biological methods for treatment of water and wastewater
are aerobic/anaerobic lagoons, oxidation ponds, activated sludge process, tricking filters, and
rotating biological contractors (Mohamed, 2015). An overview of various biological treatment
methods employed for organic compounds are shown in Fig. 1.1.
Aerobic degradation processes occur in the presence of oxygen are considered relatively
simple, inexpensive and are dependent on the operation parameters such as pH, temperature,
aeration, nutrient sources etc. (Dobson and Burgess, 2007). Aerobic microorganisms have more
potential toward toxic organic compounds and they grow faster after utilizing carbon and
energy source from organic pollutants (Surkatti and El-Naas, 2014). However, higher energy
consumption, excess sludge productions, relatively larger footprint are the major disadvan-
tages of aerobic processes (Giesen et al., 2013). The anaerobic processes are more attracting
owing to their lower cost of treatment, energy production, and less sludge generation (Banu
et al., 2008; Chowdhury et al., 2010). The higher organic contents of wastewater generated
from different sources are more suitable for anaerobic process due to their higher potential for
energy production (Sun et al., 2012).
4 1. Integration of photocatalytic and biological processes for treatment of complex effluent

FIGURE 1.1 Biological treatment methods for removal of micropollutants.

1.2.1 Activated sludge process

The most common biological treatment method employed for both industrial and domestic
wastewater is ASP. In an ASP the nutrient removal is achieved primarily by the microbial
activity that oxidizes the carbon-rich compounds. However, the organics or the inorganics
can also be removed through nonoxidative mechanisms, such as adsorption- and storage-
based methods. Storage-based methods are typically employed for enrichment of microbial
community capable of producing valuable products, such as biodiesel or bioplastic (Modin
et al., 2016). Primary degradation mechanisms in an ASP are by microbial degradation or
adsorption by microbial flocs. Most crucial phenomenon in an ASP is the simultaneous
metabolism of various pollutants by the microbial consortia present in the system. Various
micropollutants have been employed for testing the degradation capacity of ASP (Falås et al.,
2013). However, combining ASP with other treatment methods, such as, advanced oxidation
processes (AOPs) could be beneficial as ASP alone typically cannot achieve the treatment
efficiency required to meet the discharge standard. Moreover, a larger area for the setup is
required by the ASP process (Kanaujiya et al., 2019).

1.2.2 Anaerobic digestion

Anaerobic digestion is a sequence of processes by which microbes breakdown the organic
matter present in the wastewater in the absence of oxygen. Hydrolysis, acidogenesis, acetogen-
esis, and methanogenesis are the four successive biological processes involved in the anaerobic
digestion of organic matter (Bernet and Béline, 2009). Complex polymers are converted into
monomers in the hydrolysis step followed by their transformation volatile fatty acids in
 1.2 Biological treatment of organic contaminants 5
acidogenesis step. The biogas composed of CH4 − and CO2 are the end products of AD process
which can be used as an energy source.

1.2.3 Trickling bed filter/bioreactor

Trickling bed bioreactor is another process that has been commonly employed for treating
organic pollutants. In the system, the wastewater to be treated is passed through a bed
containing biomass immobilized on a supporting matrix. Trickling bed filters have employed
commonly for removal of organic pollutants, such as, PPCPs, from the wastewater. Kasprzyk-
Hordern et al. (2009) evaluated the removal efficiency of various pharmaceuticals and po-
tential EDCs from surface water and wastewater, wherein the authors also compared the
performance of trickling bed filter and ASP. The treatment process was continued for a period
>5 months. However, for most of the tested compound a removal efficiency of not greater than
50% was observed (Kasprzyk-Hordern et al., 2009).

1.2.4 Membrane bioreactor

Membrane bioreactors (MBRs) have been employed typically in either side stream con-
figuration. However, in order to overcome the configurational challenges in the side stream
configuration submerged configuration was developed. In a side stream MBR the membrane
module is placed outside the reactor unit. This setup thus demands an additional requirement
of a recirculation pump that facilitates recirculation of feed to the membrane module from
the bioreactor. This thus makes the setup energy-intensive and thereby increases the cost.
However, in case of submerged MBR configuration, the working reactor unit contains the
membrane module within (Le-Clech et al., 2005). This configuration thus facilitates the feed
or the effluent to pass through and thus allowing simultaneous treatment of the organic
pollutants.
Major mechanisms in the removal of micropollutants from MBR are physical retention, air
stripping, and biodegradation, and the two major parameters critical for the MBR performance
are sludge retention time (SRT) and hydraulic retention time (HRT; Sipma et al., 2010). Maeng
et al. (2013) reported high degradation efficiency of pharmaceuticals, such as, ibuprofen and
acetaminophen at an SRT of 8 days. The study also highlighted the influence of SRT and HRT.
However, under similar conditions removal efficiency of pharmaceuticals, such as diclofenac
and carbamazepine, was not much.

1.2.5 Moving bed biofilm reactor

Moving bed biofilm reactor (MBBR) system similar to trickling bed bioreactor is a biofilm-
based system, wherein biofilm is supported on small (1–4 cm) support matrix. This support
material enhances the surface area available for the growth of the biofilm. Also, MBBR has
been proposed to be a possible alternative for conventional biological treatment, such as, ASP.
The reason for choosing MBBR over ASP is attributed to its advantages. Major advantages
of MBBR are it is the configuration is simple and requires less space compared to that of
an ASP, also improved SRT for organisms that are slow growing. Moreover, anaerobic and
aerobic environment can be maintained in the same reactor. Thus, MBBR is also a method
6 1. Integration of photocatalytic and biological processes for treatment of complex effluent

of choice for the treatment of micropollutants from wastewater (Luo et al., 2015). Casas
et al. (2015) compared the removal efficiency of MBR and MBBR for 21 different organic
compounds. It was observed that MBBR was capable of 20% higher degradation efficiency
in comparison with the MBR under the same operating conditions. Luo et al. (2014) studied
the removal efficiency of PPCPs namely, ibuprofen, salicylic acid, primidone, and naproxen
employing MBBR that comprised of biosupport material in the form of sponge pieces. A
removal range of 81–93% was observed in the same system, the highest removal efficiency was
observed for ibuprofen (93.7%) and the lowest was observed for naproxen (81.1%). Moderate
removal efficiency (50–70%) was observed for ketoprofen, metronidazole, acetaminophen, and
gemfibrozil in the same MBBR system. However, MBBR suffers from a major drawback, that
is, the requirement of intermittent monitoring of microbial activity and also persistent need of
an aeration line.

1.3 Photocatalytic degradation of organic contaminants

Photocatalysis is one of the promising AOPs in which the degradation of organic contami-
nants occurs through the reaction with reactive oxygen species produced (hydroxyl [OH· ] and
superoxide radicals [O2 ·– ]) in the presence of photocatalyst and light source such as artificial
UV or visible lights and natural solar light (Divyapriya et al., 2021). Semiconductors such
as titanium dioxide (TiO2 ), zinc oxide (ZnO), cadmium sulfide (CdS), ferric oxide (Fe2 O3 ),
tungsten trioxide (WO3 ), and bismuth vanadate (BiVO4 ), etc. are the commonly used photo-
catalysts (Chong et al., 2010; Zhang et al., 2020). TiO2 is widely applied to treat different real
and synthetic wastewaters owing to its admirable characteristics such as chemical stability,
nontoxicity, ease of availability and low cost. Photocatalysts are employed in the heterogenous
phase either as immobilized bed or suspended particles in the liquid phase. Degussa P25 is
the commercially available TiO2 , composed of the crystalline structures anatase and rutile in
the ratio of 4:1 (Bahri et al., 2018). Contaminant’s transformation reactions occur on the surface
of the photocatalysts under the light source. The photocatalytic oxidation mechanism of TiO2
is represented in Fig. 1.2. When the UV light energy (hυ) greater than the bandgap energy
(Eb ) of photocatalyst (TiO2 ) is irradiated, an electron from the valence band is promoted to the
conduction band (ecb – ), leaving the positive vacancy hole behind (hvb + ) (Eq. (1.1)) (Chong et al.,
2010). The holes in the valence band react with water molecules and hydroxide ions to produce
·
OH radicals, which is the main oxidizing species (Eqs. (1.2) and (1.3)). Further, the holes can
also react with the organics (R) to produce oxidized products (Eq. (1.4)). Photoexcited electrons
further react with dissolved oxygen molecules to produce superoxide radicals as represented
in Eq. (1.5) (Divyapriya et al., 2021).
TiO2 + hυ → e− +
cb + hvb (1.1)
h+
vb + H2 O → ·OH + H
+
(1.2)
h+ −
vb + OH → ·OH (1.3)
+
h+
vb + R → Rox (1.4)
e− −·
cb + O2 → O2 (1.5)
 1.4 Need for integrated process for treatment of complex effluent 7

FIGURE 1.2 Photocatalytic reaction mechanisms of radical species production and contaminant oxidation
(adapted with permission obtained from Chong et al., 2010, Elsevier (2010)).

The performance of photocatalytic oxidation is affected by different factors such as catalyst

loading, pH, contaminant nature and concentration, and presence of other radicals scavenging
species (Singh and Borthakur, 2018). Loading of photocatalyst need to be optimized to get
the desired treatment efficiency since a higher amount of catalyst can also impose other
undesired effects such as light scattering, screening effect, and decreasing specific activity
(Gaya and Abdullah, 2008). It reduces the capacity of photocatalyst for photon absorption
and contaminant adsorption. Solution pH is an important factor in optimizing the treatment
efficiency since it regulates the surface charge of the photocatalyst and the oxidation potential
of the radical species. Further, a high concentration of the contaminants in the solution can
saturate the surface of the photocatalyst, which in turn decreases the photonic efficiency (Singh
and Borthakur, 2018).

1.4 Need for integrated process for treatment of complex effluent

A significant amount of wastewater generated from industries contains complex organic
compounds that are recalcitrant in nature. Though biological treatment processes are econom-
ical treatment options for the removal of organic compounds, they do not provide satisfactory
results while treating complex effluents with the increase in discharge constraints. Also, these
industrial effluents may contain higher COD loads with very less potential for biodegradation.
8 1. Integration of photocatalytic and biological processes for treatment of complex effluent

Based on the nature of industrial effluents, AOPs generating nonselective · OH radicals with
higher oxidation potential can easily oxidize organic compounds. Nevertheless, the higher
cost associated with AOPs for complete mineralization of pollutants and the toxicity of
the intermediates formed during the degradation processes necessitates the employment of
hybrid treatment processes. Also, the degradation intermediates that are nonbiodegradable or
more toxic than the parent compound make the treatment process more complex (Marsolek
et al., 2008). In this regard, the cost and difficulties caused due to the complexity of industrial
effluents necessitates hybrid treatment processes to achieve comprehensive removal of pollu-
tants (Yongrui et al., 2015). The combination of AOPs with biological processes could improve
the overall process efficiency and results in an effective treatment of complex wastewater
effluent (Paździor et al., 2019). It has been observed that ozone based and Fenton processes
combined with biological treatment techniques enhances the treatment efficiency as well as
the integration of these methods with biological treatment techniques are found to be cost
effective. Also the combined synergistic relation between both the treatment methods could
be employed at an industrial scale for complex matrices (Paździor et al., 2019). Also, the
combination of treatment employed should be based on the target removal efficiency required.
Cassano et al. (2011) observed that when a COD level of 160 mg/L was to be achieved while
treating municipal landfill leachate, combination of sequencing batch biofilter granular reactor
with solar photo-Fenton showed improved reduction in toxicity as well as the method was
most cost-effective.

1.5 Combined photocatalysis and biological process

Heterogeneous photocatalysis are powerful and efficient treatment technologies for the
transformation of hazardous organic compounds to less toxic compounds (Zeghioud et al.,
2016). They can be used as an efficient pre-/post-treatment for biological process owing
to their ability to produce radicals under irradiation in the presence of catalyst/oxidants.
Several studies have reported on the ability of photocatalysis to treat wastewater with a higher
biological load and to achieve higher biodegradability. The integration of photocatalysis as
pre-/post-treatment for biological processes are chosen based on the inherent characteris-
tics of wastewater generated and their composition (Bahri et al., 2018; Bhatia et al., 2018).
Though, the sequential coupling of the biological and photocatalytic processes are efficient
for organic compound removal, the intimate coupling approach where both the treatment
process occurring in close proximity may also improve the rapid degradation of compounds
(Marsolek et al., 2008). One of the major challenges employing photocatalysis is separation
of the photocatalyst, such as TiO2 from the slurry. This operational constraint thus increases
the associated cost for separation of the catalyst. Thus, over the years researchers have
developed and tested immobilization or impregnation of the photocatalyst on an inert support
matrix, such as chitosan (Chaturvedi et al., 2021; Mukherjee et al., 2014). It was observed
that chitosan matrix made the photocatalyst stable on the biomatrix which thereby facilitated
easy separation from the slurry along with enhanced adsorption of the pollutant (Abdelaal
and Mohamed, 2013). Considering all these facts, in this section the various approaches of
integration of photocatalysis with the biological process for the removal of organic pollutant
from wastewater are discussed. A systematic understanding of the operational parameters
 1.5 Combined photocatalysis and biological process 9

of both photocatalysis and biological processes is required to design the process to achieve a
comprehensive removal of wastewater (Marsolek et al., 2014).

1.5.1 Photocatalysis as pretreatment

Chemical pretreatment methods improve the biodegradability of wastewater before it
enters the biological treatment unit and makes it more amenable for biological degradation. In
general, AOPs improve the biodegradability of wastewater by reducing the COD. Hence, pre-
treatment of complex effluents with pharmaceuticals, pesticides, endocrine-disrupting chem-
ical, etc. are required since these compounds may inhibitorily affect the bacterial metabolism.
The use of photocatalysis as pretreatment for complex effluents improves the biodegradability
of the wastewater by producing easily degradable intermediates (Xu et al., 2015). Table 1.1
summarizes the application of photocatalysis as pretreatment for the biological process for
the degradation of organic pollutants.
A sequential photocatalysis-activated sludge-based biological system was used for the
degradation of simulated pharmaceutical wastewater (Bhatia et al., 2018). The results from
the studies inferred that the photocatalysis process as pretreatment accelerated the chemi-
cal oxidation of organic compounds and improved the biodegradability of the wastewater
from 0.23 to 0.4 after 4 h treatment. Further, the combined process resulted in an overall
COD removal of 90.5% after 4 h or photocatalysis followed by 48 h biological treatment. In
another study, photocatalysis was used as a pretreatment for a biological treatment using a
rotating biological contactor (RBC) for real pharmaceutical wastewater (Talwar et al., 2018).
The operational parameters for the photocatalysis process were optimized using a Box–
Behnken design and biodegradability enhancement from 0.178 to 0.51 was observed at an
optimized condition of TiO2 dosage of 0.6 g/L, pH = 3.20 and degradation time of 455
min. Further, the treatment of wastewater in RBC improved the COD removal to achieve a
maximum of 96.5% and achieved quality of effluent within the discharge limit. Similar to
these studies, Aissani et al. (2018) compared the photocatalytic efficiency of TiO2 and ZnO
as pretreatment for an activated sludge process for the removal of sulfamethazine. Though
an enhancement in the biodegradability was observed with pretreatment, the BOD5 /COD
ratio of only 0.25 was observed after the pretreatment process. Further, coupling the process
with the biological process resulted in an overall COD removal of 58% after 27 days of
treatment.
The photocatalysis pretreatment also reduces the complexity of the wastewater and allows
the microbes to attack the organic compound during the subsequent biological processes.
In a study conducted by Waghmode et al. (2019), the sequential photocatalytic process
followed by the biological process using a microbial consortium of Galactomyces geotrichum
and Brevibaccilus laterosporus species effectively removed methyl red from water. Though
photocatalysis alone was capable of decolorizing the dye to an extent, the microbial activity
enhanced the breakage of the azo bond and resulted in reducing the COD and toxicity of
wastewater. In another study, real dairy wastewater containing complex aromatic compounds
were pretreated using photocatalysis prior to aerobic digestion to improve the biodegradabil-
ity of the wastewater (Alafif et al., 2019). CuO-graphene oxide/TiO2 composite catalyst was
used for the photocatalytic study and the total COD of the wastewater was reduced from
14,700 to 12,747 mg/L after 6 h of treatment. The digestibility of the pretreated wastewater
10 1. Integration of photocatalytic and biological processes for treatment of complex effluent

TABLE 1.1 Photocatalysis as pretreatment for biological processes.

Pollutant Biological process Highlights of the study References

Atrazine Biodegradation using Photocatalytic pretreatment improved the Chan et al. (2004)
the bacterial species degradation efficiency of the compound and
Sphingomonas capsulata complete removal of the compound was
observed during biodegradation

4-Chlorophenol Activated sludge Higher concentration (400 mg/L) of Goel et al. (2010)
process 4-chlorophenol were completely mineralized
within 96 h of combined treatment

Tetracycline Activated sludge The pretreatment resulted in reducing the COD Yahiat et al. (2011b)
Tylosin process content and eventually the toxicity of the
compounds reduced with biodegradation
Acid Red 183 Microbial consortium Owing the toxicity and lack of mineralization Chebli et al. (2011)
by the pretreatment process, the integrated
process failed to achieve complete degradation
of the dye
Fishmeal processing Biofilms with bacteria The integrated process improved the TOC Yeber et al. (2012)
wastewater removal to 76.5% when compared to 39%
during the biological process
Coal gasification Moving bed biofilm Process integration improved the COD removal Xu et al. (2015)
wastewater reactor efficiency in a shorter duration
Bezacryl yellow dye Activated sludge Pretreatment improved the biodegradability of Khenniche et al.
treatment wastewater and enhanced the mineralization (2015)
2-Chlorophenol in Anaerobic oxidation Pretreatment improved the biodegradability Anjum et al. (2018)
sewage sludge and the efficiency of methane production
increased
Wastewater from Biofilm on biocarrier Rapid degradation of organic compounds with Chavan and
common effluent the removal of 61% and 92% COD and BOD, Fulekar (2018)
treatment plant respectively
Sulfamethazine Activated sludge The biodegradability enhanced during the Aissani et al. (2018)
culture pretreatment improved the pollutant and COD
removal
Pharmaceutical Activated sludge Photocatalysis pretreatment improved the Bhatia et al. (2018)
effluent containing treatment biodegradability of wastewater from 0.23 to 0.4
atenolol and the combined process resulted in 90.5%
COD removal
Sulfamethoxazole Sequencing batch The photocatalysis pretreatment resulted in Cai and Hu (2018)
trimethoprim reactor achieving 90% removal of pollutants and
restricted the development of antibiotic
resistance in the subsequent biological process
due to the intermediates formed
Industrial textile Aerobic biological Coupled process extended the color removal da Silva et al. (2019)
wastewater treatment efficiency and TOC reduction
(continued on next page)
 1.5 Combined photocatalysis and biological process 11
TABLE 1.1 Photocatalysis as pretreatment for biological processes—cont’d

Pollutant Biological process Highlights of the study References

Methyl red dye Microbial consortium Complete decolorization of 500 mg/L of dye Waghmode et al.
of Galactomyces was observed within 4 h of combined process (2019)
geotrichum and when compared to 6 h for the biological process
Brevibaccilus
laterosporus species
Triazine-containing Biodegradation using The photocatalysis pretreatment improved the Chan et al. (2019)
pollutants K. pneumoniae species biodegradability of the wastewater and resulted
in complete mineralization of the pollutant after
the combined process
Chlorophenol Activated sludge Pretreatment process improved the Bobirică et al.
biodegradability to achieve complete (2020)
transformation of parents compounds after
biological process
Agricultural Anaerobic digestion Combined process improved the COD removal Becerra et al. (2020)
wastewater with of the wastewater by 72.2% when compared to
chlorpyrifos 46.6% during the biological process
Reactive Green 12 Activated sludge An enhancement in the COD removal along Zeghioud et al.
with toxicity reduction was observed during the (2020)
combine photobiological process
Oilfield produced Granular bioreactor The integrated solar photocatalytic granular Golestanbagh et al.
water bioreactor enhanced the overall COD removal (2020)
by 44%
Landfill leachate Biological treatment Higher COD removal with heavy metal removal Yasmin et al. (2020)
using Candida was observed during the combined process
tropicalis strain

was improved and the subsequent aerobic digestion resulted in 98.9% total COD removal in
27 days of treatment.
The pretreatment of complex wastewater effluents with photocatalysis can often reduce the
overall treatment cost and time for biological process. In a study conducted by Zangeneh et al.
(2014), an immobilized photocatalytic reactor under UV irradiation was effectively improved
the biodegradability of wastewater generated from linear alkylbenzene (LAB) production and
reduced the treatment time of biological treatment time from 84 h to 12 h. The biodegradability
index of wastewater was increased by 3.5 times after 4 h of irradiation and the pretreated
feed was treated continuous feeding intermittent discharge bioreactor to achieve 80% COD
removal efficiency. The process integration also reduced the turbidity and reduced the wastage
of sludge during the biological process.
Landfill leachates are also a source of complex effluents with varying concentrations and
volume that changes with time. Raw leachate collected from a municipal landfill within
the region of Upper Silesia in Poland was pretreated in a photoreactor with a medium-
pressure mercury lamp and P25 as the catalyst (Wiszniowski et al., 2006). Even though the
solution matrixes interfered with the photocatalytic activity, a considerable improvement in
12 1. Integration of photocatalytic and biological processes for treatment of complex effluent

the biodegradability of the leachate was observed after photocatalysis treatment. Further,
the successive aerobic activated sludge system reduced the final COD of the effluent to the
permissible discharge of 125 mg/L.
Though the integrated processes were effective for organic pollutant removal, the technol-
ogy had failed often due to the composition of wastewater. In a study conducted by Chebli
et al. (2010), enhanced performance of the photocatalytic pretreatment process substantially
reduced the COD load of the wastewater containing a mixture of dyes. However, due to the
higher characterization yield, the BOD/COD ratio remained almost constant and the efficiency
of the biological process is reduced. Further, the toxicity of intermediates formed during the
pretreatment also hindered the biological process. A similar unfavorable trend in the degrada-
tion of a fungicide, cyproconazole was observed by Yahiat et al. (2011a) during the integrated
photocatalysis followed by biological treatment using a pure bacterial culture of Pseudomonas
fluorescens bacteria. Though they have observed an enhancement in the mineralization of the
compound during the pretreatment, the toxicity of the compound did not decrease due to the
formation of photocatalysis intermediates.

1.5.2 Photocatalysis as post-treatment

Biological processes are generally cost-effective and are capable of degrading wastewater
rich in higher BOD (Chavan and Fulekar, 2018). However, the micropollutants that are
recalcitrant in nature are not effectively removed after biological treatment. In this regard,
a highly effective polishing treatment step to remove these contaminants are required be-
fore discharging of the treated effluents (Moussavi et al., 2019). The photocatalysis process
as post-treatment for a biological process can necessarily achieve degradation of toxic mi-
cropollutants and the integrated process could ensure an economic optimization for the
wastewater treatment (Mabuza et al., 2017). In a study conducted by Gimeno et al. (2016),
wastewater containing a mixture of pharmaceuticals was treated by an aerobic biological
treatment followed by solar photocatalysis. Though the biological process was ineffective in
removing the recalcitrant pharmaceuticals, the integration with photocatalysis enhanced their
removal due to the formation of · OH radicals. The photocatalytic process efficiency was further
enhanced when the process was combined with ozonation process. Similarly, for another
study, industrial textile wastewater was treated in a fungal membrane bioreactor followed
by a post-treatment using photocatalytic membrane reactor to achieve 93% and 99% color
and COD removal, respectively (Deveci et al., 2016). Though the fungal degradation using
Phanerochaete chrysosporium species was effective for COD reduction, poor color removal was
observed without process integration.
While dealing with complex effluents in small-scale reactors, the biological processes
followed by photocatalysis were found to be more efficient owing to the production of toxic
products during photocatalysis pretreatment. Further, the operational cost associated with the
photocatalysis process to achieve complete mineralization requires prolonged irradiation and
may also result in the disappearance of active molecules for biological processes (Kim and
Park, 2008). Sharma and Philip (2016) studied the effect of an integrated bioreactor system
as a pretreatment for photocatalysis for the removal of real coke oven wastewater (CWW).
The biological system comprised of a sequence of anaerobic–aerobic–anoxic process and was
effective in removing a maximum of 78.5% COD. Further, the UV–photocatalysis system
 1.5 Combined photocatalysis and biological process 13

improved the quality of wastewater by enhancing the COD removal to 96.2%. The reactive
oxidizing species generated during the polishing photocatalysis process also resulted in the
removal of the color of CWW with a treatment time of 240 min. In another study, a mixture
of chlorophenols was pretreated in an activated sludge flow biological treatment followed
by circulative mode photocatalytic treatment under black light or sunlight (Suryaman and
Hasegawa, 2010). The combined process reduced the overall treatment time and resulted in
the complete degradation of pollutants under solar irradiation.
The higher organic load of wastewater generated from agro-based industries or dairy
industries are often pretreated with a biological process to minimize the cost of chemical
treatment. In a study conducted by Banu et al. (2008), dairy wastewater was treated a hybrid
up-flow anaerobic sludge blanket reactor (HUASB) of laboratory-scale followed by a solar
photocatalysis process. The anaerobic process was effective in removing 84% of COD load in
a shorter HRT of 5.9 h and its integration with the photocatalytic process resulted in overall
95% COD removal. In another study, the wastewater effluent generated from nitrocellulose
industry was treated with the combination of a fungal-based biological process followed by a
photocatalysis process (Barreto-Rodrigues et al., 2009). The lignin-derived organic compounds
were easily degraded by the Aspergillus 2NBL1 fungal species involving multiple biochemical
reactions to form biodegradable intermediates. These intermediates of chromophore com-
pounds were more prone to the photocatalytic process and resulted in 94.2% decolorization as
well as 92.6% total phenol removal. Similar to the above studies, when UV photocatalysis
was used as a post-treatment option for anaerobic digestion of real distillery effluent and
raw molasses wastewater, an enhanced COD removal was observed when compared to the
pretreatment option (Apollo et al., 2013).

1.5.3 Multistep processes

The main purpose of multistep processes is to reduce the cost of photocatalysis. Though
the photocatalytic treatment of wastewater is considered as a promising methodology to
remove recalcitrant organics, it requires a high amount of energy and oxidants (Elmolla and
Chaudhuri, 2011). In the case of a two-step process with photocatalysis as post-treatment,
the photocatalysis process must ensure the complete mineralization of organics which are
not removed in the biological process. In the multistep process, the photocatalysis process
is located in between two or more biological processes (Paździor et al., 2019). Recalcitrant
organics that are not degraded in the first stage of the biological process is introduced to the
photocatalysis step, leading to the transformation of recalcitrant organics into biodegradable
compounds which are further mineralized by the biological process in the final step (Paździor
et al., 2019). Biologically pretreated coal gasification wastewater was further treated by the
combined heterogeneous photocatalysis and moving bed biofilm reactor (MBBR) processes
(Xu et al., 2015). TiO2 immobilized sewage sludge-based activated carbon was used as a
catalyst to treat the biologically pretreated wastewater effluent. The photocatalysis step im-
proved BOD5 /COD from 0.08 to 0.49 ensuring the conversion of recalcitrant organics into
biodegradable compounds. Further integration of MBBR as final step, initial TOC of 120
mg/L was reduced to 11.8 mg/L in 9 h. Treatment of wastewater by direct MBBR without
photocatalysis process decreased the TOC to 40 mg/L in 20 h. The removal efficiencies were
found to be about 93.4% for BOD5 , 87.3% for COD, 89.6% for total phenol, and 77.2% for total
14 1. Integration of photocatalytic and biological processes for treatment of complex effluent

nitrogen for the integrated process while MBBR alone exhibited only 57.1%, 44.4%, 40.9%, and
50.5%, respectively (Xu et al., 2015).

1.6 Mineralization and toxicity reduction

Toxicity assessment is crucial to optimize the treatment process when the complete min-
eralization is not aimed to attain (Rueda-Marquez et al., 2020). These assessment studies can
indicate when the toxicity is developed and disappeared in the system during the treatment
process. Evaluation of toxicity is a must when the photocatalytic process is intended to be
implemented. Toxicity studies that are applied during the photocatalytic detoxification of
wastewaters such as (i) bacteria-based assays including bioluminescence’s assay with Vibrio
fischeri, Ames test with Salmonella typhimurium and Kirby–Bauer method of zone inhibition
with E. coli (Rueda-Marquez et al., 2020); (ii) freshwater invertebrates-based immobilization
test with Daphnia magna (Brienza et al., 2016); (iii) microalgae growth inhibition assay with
green algae Pseudokirchneriella subcapitata and blue–green algae Anabaena flos-aquae (He et al.,
2016); (iv) plant-based phytotoxicity test using the seeds of Sorghum saccharatum, Lepidium
sativum, Sinapis alba, etc. (Tsoumachidou et al., 2017); and (v) estrogenic test (HELN ERα
cell line), and genotoxicity assessment (LS 174T cell line; Brienza et al., 2016). Most of the
studies reported a reduction in the toxicity of wastewater effluents after the treatment with
photocatalysis. However, very few bioassays carried out with Vibrio fischeri (Vela et al., 2018a),
Daphnia magna (Çifçi and Meriç, 2015), and Ames test (Saverini et al., 2012) reported the
increase in toxicity of wastewater after the treatment mainly due to the following factors: (i)
possible production of toxic intermediates than the parental compounds, (ii) synergistic toxic
effect resulted due to the presence of various contaminants, and (iii) possible occurrence of
photodissolution of photocatalysts (Vela et al., 2018a, 2018b). In the case of hybrid photocatal-
ysis, further toxicity can be attributed to the addition of chemicals such as hydrogen peroxide.
Elimination of these toxic residual chemicals from the treated effluents is essential for safer
discharge or reuse.
Among other tests, bioluminescence’s assay with Vibrio fischeri is widely used in many
studies (Rueda-Marquez et al., 2020). Simulated industrial wastewater spiked with 213 mg/L
of ibuprofen showed 73.9–78.3% of luminescence inhibition before treatment. While the
inhibition was reduced to 30.3–40.8% for the 50% mineralization of ibuprofen in TiO2 /UV-LED
system at 240 min (Jallouli et al., 2018). Removal of endocrine disruptors in sewage wastewater
effluents using photocatalysts TiO2 and ZnO was studied under sunlight in the presence of
Na2 S2 O8 as electron acceptor (Vela et al., 2018a, 2018b). After the photocatalysis treatment,
Vibrio fischeri toxicity was reduced from ∼60% to ∼15% with TiO2 P25 (Vela et al., 2018a).
In case of ZnO photocatalyst, for the removal of 83% dissolved organic carbon, only 11%
inhibition of bioluminescence was observed (Vela et al., 2018b). Though some studies reported
the inhibition of Vibrio fischeri even at low concentrations of contaminants ranging from ng/L
to μg/L, a few studies showed low sensitivity to the large number of detected contaminants
in municipal wastewater with the EC50 value of 80% (Brienza et al., 2016). According to
Calleja et al. (1986), effluents exhibiting the EC50 of >75% is considered as nontoxic. It shows
that the toxicity assays with Vibrio fischeri may not be sensitive with the real wastewater
 1.7 Pilot-scale integrated process 15
effluents consisting of micropollutants (Rueda-Marquez et al., 2020). Similarly, municipal
wastewater effluent showed the EC50 of 98% with Pseudokirchneriella subcapitata-based assay.
While wastewater spiked with the pollutants in the concentration range of mg/L showed
higher sensitivity (Brienza et al., 2016; He et al., 2016). Though, the widely used assays had not
shown toxicity of the wastewater detected with 53 micropollutants including pharmaceuticals,
pesticides, and others, the estrogenic assay was able to detect relevant estrogenic compounds
even with low concentrations (Brienza et al., 2016).
Most of the studies used TiO2 as a photocatalyst since it possesses the characteristics of ideal
photocatalytic material. Whereas ZnO exhibits the important drawback of photocorrosion
during the treatment. Photodissolution of Zn during the treatment of sewage wastewater
effluent increased the toxicity in Vibrio fischeri assay at the Zn2+ concentration of 186 ± 8 μg/L
(Vela et al., 2018b).

1.7 Pilot-scale integrated process

Coupling of photocatalytic system with biological processes are very effective in terms of
mineralization and toxicity reduction under laboratory studies. Nevertheless, the practical
applicability of the integrated processes for removing complex effluents is less explored due
to the difficulty in the treatment of a large volume of wastewater, catalyst recovery, and
other experimental conditions. These pilot-scale studies would help in understanding the
real problems faced in respect of wastewater generating from different industries (Sarria
et al., 2003). A solar photocatalytic process combined with a pilot-scale aerobic immobilized
biomass reactor was employed to enhance the mineralization of an industrial pollutant
α-methylphenylglycine. The solar photocatalytic process that occurred in the compound
parabolic collector with the addition of Fenton reagents improved the biodegradability of the
wastewater to produce biocompatible intermediates and results in 95% overall mineralization.
Another study conducted by Sathya et al. (2019) evaluated the process efficiency advanced
oxidation process with membrane bioreactor for the removal of real textile wastewater in
a pilot-scale plant. Among the AOPs used, ozonation and visible light photocatalysis using
WO3 catalyst improved the biodegradability of wastewater and helped in reducing the fouling
of MBR. Further, the integrated system achieved 93% COD removal to meet the permissible
discharge limit of wastewater. Similarly, in a study conducted by Cassano et al. (2011) the
researchers compared various AOPs and biological treatment methods and conducted a
cost analysis. It was observed that in order to achieve a COD value of 160 mg/L for the
effluent combination of sequencing batch biofilter granular reactor (SBBGR) and solar photo-
Fenton (SphF) process was most cost effective, while with higher COD values (500 mg/L)
to be achieved treatment methods compared were relatively similar with respect to cost.
The economic analysis for the pilot-scale study was even though approximate can further be
applied at industrial scale (Cassano et al., 2011). In a similar study conducted by Almomani
et al. (2018) it was observed that combined photocatalytic oxidation enhanced the biodegrad-
ability of dichloromethane. This further highlights that combined processes enhance the
removal efficiency of the pollutant also it reduces the overall footprint that is required for the
setup.
16 1. Integration of photocatalytic and biological processes for treatment of complex effluent

1.8 Conclusion
The improper discharge of industrial effluents containing complex organic compounds in
water streams has potential impact on ecosystem. Owing to the persistence of these pollu-
tants, the conventional wastewater treatment technologies are not effective for their complete
removal. Though advanced oxidation processes are efficient to oxidize these pollutants,
the technologies are economically unviable and nonsustainable for complex effluents. The
integration of photocatalysis with biological processes could be an appropriate method which
could oxidize the organic compounds present in the complex effluents. The photocatalysis
process can break down the molecular structures of refractory organics and convert them to
biodegradable forms for biological processes when it is used as a pretreatment. At the same
time, photocatalysis process acts as a polishing step to reduce the hazardous nature of biolog-
ically treated wastewater by oxidizing the organic compound present during post-treatment
application. The integration of photocatalysis with biological processes as pre-/post-treatment
depends upon the characteristics of the wastewater generated. Though, sequential coupling of
biological and photocatalytic processes is efficient for organic compound removal, the intimate
coupling approach where the both the treatment process occurring in close proximity may
improve the rapid degradation of compounds.

References
Abdelaal, M.Y., Mohamed, R.M., 2013. Novel Pd/TiO2 nanocomposite prepared by modified sol-gel method for
photocatalytic degradation of methylene blue dye under visible light irradiation. J. Alloys Compd. 576, 201–207.
https://doi.org/10.1016/j.jallcom.2013.04.112.
Aissani, T., Yahiaoui, I., Boudrahem, F., Ait Chikh, S., Aissani-Benissad, F., Amrane, A., 2018. The combination
of photocatalysis process (UV/TiO2 (P25) and UV/ZnO) with activated sludge culture for the degradation of
sulfamethazine. Sep. Sci. Technol. 53, 1423–1433. https://doi.org/10.1080/01496395.2018.1445109.
Alafif, Z.O., Anjum, M., Kumar, R., Abdelbasir, S.M., Barakat, M.A., 2019. Synthesis of CuO–GO/TiO2 visible light
photocatalyst for 2-chlorophenol degradation, pretreatment of dairy wastewater and aerobic digestion. Appl.
Nanosci. 9, 579–591. https://doi.org/10.1007/s13204-018-0921-7.
Almomani, F.A., Bhosale, R.R., Khraisheh, M.A.M.M., Kumar, A., Kennes, C., 2018. Mineralization of dichloromethane
using solar-oxidation and activated TiO2 : pilot scale study. Sol. Energy 172 (2). https://doi.org/10.1016/j.solener.
2018.07.042.
Anjum, M., Kumar, R., Barakat, M.A., 2018. Synthesis of Cr2 O3 /C3 N4 composite for enhancement of visible light
photocatalysis and anaerobic digestion of wastewater sludge. J. Environ. Manage. 212, 65–76. https://doi.
org/10.1016/j.jenvman.2018.02.006.
Apollo, S., Onyango, M.S., Ochieng, A., 2013. An integrated anaerobic digestion and UV photocatalytic treatment of
distillery wastewater. J. Hazard. Mater. 261, 435–442. https://doi.org/10.1016/j.jhazmat.2013.06.058.
Ayed, L., Asses, N., Chammem, N., Ben Othman, N., Hamdi, M., 2017. Advanced oxidation process and biological
treatments for table olive processing wastewaters: constraints and a novel approach to integrated recycling
process: a review. Biodegradation 28, 125–138. https://doi.org/10.1007/s10532-017-9782-0.
Aziz, A.R.A., Asaithambi, P., Daud, W.M.A.B.W., 2016. Combination of electrocoagulation with advanced oxidation
processes for the treatment of distillery industrial effluent. Process Saf. Environ. Prot. 99, 227–235. https://
doi.org/10.1016/j.psep.2015.11.010.
Bahri, M., Mahdavi, A., Mirzaei, A., Mansouri, A., Haghighat, F., 2018. Integrated oxidation process and biological
treatment for highly concentrated petrochemical effluents: a review. Chem. Eng. Process. - Process Intensif. 125,
183–196. https://doi.org/10.1016/j.cep.2018.02.002.
Another random document with
no related content on Scribd:
 CHAPTER XLI.
DECISION OF THE UMPIRES.

A.H. XXXVII. A.D. 658.

The interval passed uneasily. Muâvia

ruled in Syria; Aly, over the rest of the The interregnum.
Moslem world. Neither, for the moment,
interfered with the other. The empire held itself in suspense.
Within the time appointed, Amru
appeared at Dûma, and, shortly after, Abu The Umpires meet.
Mûsa. Each was followed, according to Ramadhân, a.h. XXXVII.
Feb. a.d. 658.
agreement, by a retinue of four hundred
horsemen.[543] Thither also, to the neutral spot, flocked multitudes
from Irâc and from Syria, from Mecca and Medîna. With intense
interest they watched the strange proceeding, which (as they
expected) was about to decide the future of Islam. The leading chiefs
of the Coreish were also there; some, we are told, with the distant
hope that haply the choice might fall on one of themselves.[544]
The Umpires met in a pavilion pitched
for the occasion; and beneath it, a private And confer with each other.
conference was held between the two
alone. The account given by our authorities of what passed between
them, is very brief. The result we must accept, but the colloquy which
led to it is altogether of an uncertain kind. The gist of it is as follows.
Abu Mûsa, pressed by his astute colleague, admitted that the putting
of Othmân to death was a wicked and unjustifiable thing. ‘Then why,’
rejoined Amru, ‘wilt thou not take Muâvia, the avenger of blood, for
his successor?’ ‘If it were a mere question of blood-feud or
kinsmanship,’ Abu Mûsa answered, ‘there were Othmân’s sons with
a nearer claim. Succession to the throne, however, was a matter to
be determined, not by such considerations, but by the vote of the
chief Companions of the Prophet.’ Amru (so the story runs) then
proposed his own son: ‘A just and good man,’ replied Abu Mûsa, ‘but
one whom thou hast already made to take sides in the civil war; and,
Amru! we must above all things beware of kindling mutiny again
amongst the Arab tribes.’ A similar objection shut out Abdallah son of
Zobeir; and the son of Omar was put aside as not having qualities
fitting him for command. ‘Then,’ asked Amru, after all the possible
candidates had been named and negatived, ‘what may be the
judgment that thou wouldest give?’ ‘My judgment,’ answered Abu
Mûsa, ‘would be to depose both Aly and Muâvia, and then leave the
people free to choose whom they will.’ ‘Thy judgment is also mine,’
said Amru promptly; ‘let us go forth.’
The people, in breathless expectation
of the impending announcement, crowded The judgment.
round the pavilion as the Umpires issued
from it. ‘Let them know,’ said Amru to his fellow, ‘that we are agreed.’
Abu Mûsa advanced, and with voice loud and clear,[545] said: ‘We
are agreed upon a decision such as, we trust, will reconcile the
people, and reunite the empire.’ ‘He speaketh true,’ said Amru: ‘step
forth, O Abu Mûsa, and pronounce thy judgment.’[546] Then spoke
Abu Mûsa: ‘Ye people! we have considered the matter well. We see
no other course so likely to restore peace and concord amongst the
people, as to depose Aly and Muâvia, both the one and the other.
After that, ye shall choose a fit man in their room. This is my
judgment.’ He stepped aside, and Amru
advancing said: ‘Ye have heard the Deposing Aly.
sentence of Abu Mûsa. He hath deposed
his fellow; and so do I too depose him. But as for my Chief, Muâvia,
him do I confirm. He is the heir of Othmân, and as avenger of his
blood, the best entitled to succeed.’
The assembly was thunderstruck. Even
the Syrians had never dreamed of Muâvia The people thunderstruck.
achieving such a triumph; nor had it
entered the minds of those on Aly’s side, that their Umpire could be
overreached thus shamefully. ‘What could I do?’ cried Abu Mûsa,
assailed on every hand; ‘he agreed with me, then swerved aside.’
‘No fault of thine,’ said the son of Abbâs: ‘it was the fault of those
who put thee in the place.’ Overwhelmed with reproaches, Abu Mûsa
made his escape and fled to Mecca, where he thenceforward lived in
obscurity.[547] In the heat of his indignation,
the commander of the Kûfa body-guard Muâvia saluted Caliph by the
Syrians.
made an onset upon Amru, and was
roughly handling him, when the people interposed to set him free.
Amru returned forthwith to Damascus, where by acclamation Muâvia
was saluted Caliph by the Syrians.
How the startling intelligence affected
Aly, may be judged by the fact that to the The two Caliphs curse each
other in the daily service.
prescribed daily service he added a
petition cursing by their names, Muâvia, Amru, and several of their
chief adherents. Muâvia was nothing loth to follow his example. And
so the world was edified by the spectacle, in the cathedral temples of
Islam, of the rival Commanders of the Faithful uttering maledictions
in their daily prayers, the one against the other.[548]
 CHAPTER XLII.
THE KHAREJITES, OR THEOCRATIC SEPARATISTS, DEFEATED
AT NEHRWAN.

A.H. XXXVII. A.D. 658.

Aly, as the reader will suppose, was not

content with heaping imprecations on his Aly’s designs against Syria.
antagonist. He resolved on the immediate
renewal of hostilities. But he had other work before him first in
dealing with the fanatics nearer home.
Ever since they had broken up their
camp at Harôra, these, instead of settling Hostile attitude of the
down in sentiments of loyalty and peace, theocractic faction.
Ramadhân, a.h. XXXVII.
had been gaining in aggressive force and Jan. a.d. 658.
stubbornness. There should (such was
their cry) be no oath of fealty but to the Lord alone, the Mighty and
the Glorious. To swear allegiance either to Aly or Muâvia was in
derogation of that great name. ‘Ye are both of you,’ they would say,
‘coursing along, neck and neck, in the race of apostasy: the Syrians
run after Muâvia whether the way be right or wrong, and ye swear for
Aly through black and white. It is nought but blasphemy.’ So they
formulated their creed into one short sentence: No judgment, but the
Lord’s alone; and this they insolently flung in Aly’s teeth.[549] In vain
the Caliph argued, as he had done before, that the Arbitration had
been forced upon him by themselves. ‘It is true,’ they would readily
reply; ‘but we have repented of that lapse; and thou must repent of it
likewise, or else we shall fight against thee; and if so be that we are
slain, we shall meet our Lord with joy.’ Aly
yet hoped to gain them over. He bore with Aly’s forbearance.
their seditious talk; and in a public address
in the Great Mosque at Kûfa, he declared his intention of treating
them with forbearance. ‘They should have free access to the
mosques for prayer. If they joined his army, they should share the
booty like the rest. So long as they refrained themselves from any
overt act of disloyalty, he would use no force of arms against them.’
Instead of softening the fanatics, this
moderation only tended to embolden them. The Khârejites march to
Nehrwân. Shawwâl, a.h.
When the Umpires’ judgment was XXXVII. March, a.d. 658.
announced, they were elated at a result
which in their eyes amply justified their secession at Siffîn. They held
frequent meetings in secret, and resolved on raising the Divine
standard. They looked for heavenly interposition; but even if they
perished, it would be in a righteous cause, sure to triumph in the
end; they would, at any rate, be protesting against a wicked world,
and become inheritors of a blessed futurity. In the month following
the Arbitration, they began accordingly, in concert with the brethren
who sympathised with them at Bussorah, to leave their homes by
stealth. The party from Bussorah, five hundred strong, was pursued
by the governor, Ibn Abbâs; but they effected their escape, and
joined the bands which in greater force had issued forth from Kûfa.
Secular power, and the dignity and pomp of this life, were abhorrent
from these Covenanters’ creed; and it was only after many had
declined the dangerous pre-eminence, and then simply as a
temporary expedient to meet the present necessity, that a chief was
prevailed on to accept the supreme command. The design was to
occupy the city of Medâin, upon the Tigris, and there, under a
Council of Representatives, establish theocratic rule as a model to
the ungodly cities around. But the governor had timely warning, and
repulsed the attempt. They passed on, and crossed the river farther
up in various bodies, and, appointing Nehrwân as their rendezvous,
assembled there to the number of 4,000.
Aly did not at first recognise the serious
character and bearing of the movement. Aly orders levy for Syrian
campaign.
The number of the fanatics was
comparatively insignificant; and he hoped that, when they saw their
former comrades in arms marching against the graceless Syrians,
they would not hesitate again to join his standard. So he mounted
the pulpit and harangued the men of Kûfa. He reprobated the
Umpires, because they had cast the Book of the Lord, equally with
the precedent of the Prophet, behind their backs. Both were
apostates, rejected of the Lord, of his Prophet, and of all good men.
‘Wherefore,’ he concluded, ‘we must begin to fight our battle again at
the point where, on the eve of victory, we were forced to leave it off.
Prepare then to march for Syria, and be ready in your camp without
the city, by the second day of the coming week.’ Then he indited a
despatch to the fanatics at Nehrwân. It was
couched in terms similar to his address, And summons the theocrats,
and ended thus: ‘Now, therefore, when ye who refuse to join him.
have read this, return forthwith and join the army. I am marching
against the common enemy, yours and ours alike; and we have
come back again to the state of things when aforetime at Siffîn ye
were fighting by my side.’ In reply Aly received an insulting message:
‘If he acknowledged his apostasy and repented thereof, then they
would see whether anything could be arranged between them;
otherwise they cast him off as an ungodly heretic.’ The stiff-necked
theocrats were thereupon, for the present, left to their own devices,
and the business of raising levies for Syria proceeded with. But little
enthusiasm was anywhere displayed in the
cause of Aly. Of the 60,000 fighting men Aly marches for Syria.
drawing stipendiary allowances in
Bussorah, 3,000 were with difficulty got together. At Kûfa, after vain
appeal to the loyalty of the city, a conscription was ordered through
the heads of clans; and thus at length an army of threescore and five
thousand men of every rank and class was brought into the field.[550]
With this imposing force, Aly had
already commenced his march on Syria, But is diverted by the
when tidings reached him that the fanatics excesses of the fanatic host.
were committing horrid and cold-blooded outrages in the country
round about their camp.[551] A messenger was sent to make inquiry;
but he too was put to death by the insurgents. The tidings of their
proceedings became more and more alarming, and the men of Kûfa
demanded to be led against them; ‘for how,’ said they, ‘can we leave
such outlaws unpunished and at large behind us, and our homes
exposed to their unlicensed cruelties?’ Aly himself, seeing that this
must be done, changed his course eastward, crossed the Tigris, and
marched against the fanatics. When now near to Nehrwân, he sent a
messenger forward, to demand that the murderers should be
delivered up. ‘Surrender these to justice,’ he said, ‘and ye shall be
left alone, until the Lord grant us victory in Syria, and then haply He
shall have turned your hearts again toward us.’ They replied that
‘they were all equally responsible for what had passed, and that the
blood of the ungodly heretics they had slain was lawful to them.’ A
parley ensued, in which the Caliph through his captains expostulated
with the misguided fanatics, and offered quarter to all who should
come over to his army, or retire peaceably to their homes. Some
obeyed the call and came over; 500 went
off to a neighbouring Persian town, and The fanatics at Nehrwân
many more dispersed in other directions to dispersed and slain.
their homes at Kûfa or elsewhere. Eighteen hundred remained upon
the field, martyrs to the theocratic creed. With the wild battle cry, On
to Paradise! they rushed upon the Kûfa lances, and were slain to a
man. Aly’s loss was trifling.[552]
It would have been better for the peace
of Islam if none of the four thousand had The Khârejites again appear
escaped. The snake was scotched, not in the field. a.h. XXXVII. a.d.
658.
killed. The fanatic spirit was strangely
catching; and the theocratic cause continued to be canvassed
vigorously and unceasingly, but in secret, at Bussorah and at Kûfa.
However hopeless the attainment of their object might appear, the
fanatics were nerved, if not by the expectation of Divine aid, at the
least by the sure hope of a Martyr’s crown. In the following year
armed bodies once and again appeared unexpectedly in the field,
denouncing Aly, and proclaiming that the Kingdom of the Lord was at
hand. One after another these bands of insurgent fanatics were cut
to pieces, or put to flight with ease. But the effect was unsettling; and
it could not but endamage the name and power of Aly, who now
reaped the fruit of his weak compromise with the enemies of
Othmân, and his neglect to bring them to justice. Fanatical in their
extravagant doctrine, they were too sincere
to combine with any of the political sects, They become a thorn in the
and hence they never came near to Moslem empire.
leaving any permanent mark of their theocratic creed behind them.
But both at this period and in succeeding reigns, we find them at
intervals gathering up their strength to assail the empire, and as
often beaten back. Ever and anon, for years, and even for ages,
these Khârejites still ‘went forth’[553] on their desperate errand, a
thorn in the side of the Caliphate, and a terror to the well-disposed.
 CHAPTER XLIII.
REVOLT OF EGYPT.

A.H. XXXVIII. A.D. 658.

Having thus disposed of the fanatics at

Nehrwân, and recrossed the Tigris, Aly, at Aly abandons the war
the head of his army, turned his face again against Syria. End of XXXVII.
April, a.d. 658.
towards Syria. But the soldiers urged that,
before setting out upon so long a campaign, their armour needed
refitting. ‘Let us return for a little to our homes,’ they said, ‘to furbish
up our swords and lances, and to replenish our quivers.’ Aly
consenting, they marched back and pitched their camp at Nokheila.
This being close to Kûfa, the soldiers dropped off in small parties
thither; and so it came to pass that, in a short time, excepting
commanding officers, the camp was left almost empty. Aly, finding
that no man returned, became impatient, and himself re-entering
Kûfa, again harangued the people on the obligation to go forth with
him and make war on Syria. But exhortation and reproach fell
equally on listless ears. There was no response. Aly lost heart. The
Syrian expedition fell through; and no attempt was made to resume it
further.
Thus closed the thirty-seventh year of
the Hegira. The situation was unchanged. Position of Aly and Muâvia.
Muâvia, with now a colourable title to the
Caliphate, remained undisturbed in his position virtual monarch of
Syria, strong in the loyalty and affections of the province; while Aly,
mortified by an indifferent and partly alienated people, was now to
experience a severer trial.
We turn to Egypt. Before the Syrian war, as already stated, there
was a powerful faction in that dependency of Aly’s Caliphate,
especially at Kharanba, siding with those who demanded satisfaction
for the blood of Othmân; and Cays, having been recalled for leaving
these dissentients alone, Mohammed son of Abu Bekr had been
appointed in his room. Casting aside the
waiting policy of his wiser predecessor, Egypt revolts. a.h. XXXVIII.
Mohammed at once summoned the a.d. 658.
recusants, either to submit themselves to him, or to be gone from
Egypt. They refused, but masking for the present their hostile
designs, watched the issue of the struggle at Siffîn. When the armies
separated from that battle-field, leaving Muâvia still master of Syria,
they gained heart and began to assume the offensive. A party sent
against them was defeated, and the leader slain; and a second
attempt at retrieving the loss met with a like fate. The slumbering
elements of revolt were everywhere aroused.
Aly saw now the mistake which he had
made, but too late. He would have Ashtar, appointed governor,
is poisoned.
reappointed Cays; but Cays declined again
to take the post. The only other fitted for the emergency was Ashtar
the regicide, whom he summoned from his command at Nisibîn, and
sent off in haste to Egypt. But on the way he met with an untimely
death, having been poisoned, at the instigation (it is said) of Muâvia,
by a chief on the Egyptian border with whom he rested.[554] There
was joy at the death of the arch-regicide throughout the land of
Syria, where he had been greatly feared. Aly was equally cast down
by the untoward event. His only resource was now to bid
Mohammed son of Abu Bekr hold on, and do what he could to
retrieve his position. But the faction which
favoured Muâvia gained ground daily; and Mohammed killed and Egypt
when, shortly after, Amru, at the head of a conquered by Amru for
Muâvia. Safar, a.h. XXXVIII.
few thousand men, crossed the border, he July, a.d. 658.
was joined by an overwhelming body of
insurgents. Mohammed, after a vain attempt to meet his enemy in
the field, was easily put to flight. In the struggle he was killed, and his
body ignominiously burned in an ass’s skin.[555] Thus Egypt was lost
to Aly; and Amru, as the lieutenant of the rival Caliph, again became
its governor.
The loss of Egypt was the harder for
Aly to bear, as undoubtedly it might have Mortification of Aly at the
loss, and at the
been averted but for his removal of Cays; lukewarmness of Kûfa.
and even now it might have been retrieved
if the men of Kûfa had not been heartless in his cause. Over and
again he implored them to hasten to the defence of Egypt. With
difficulty two thousand men were got together; but after so long a
delay that they had hardly marched before news of the defeat made
it necessary to recall them. Aly thereupon ascended the pulpit, and
upbraided the people for their spiritless and disloyal attitude. For fifty
days, he had been urging them to go forth, to avenge their fallen
brethren, and to help those who were still struggling for him in the
field. Like a restive wayward camel, that refused its burden, they had
held back. ‘And now,’ he said, in grief and bitterness of spirit, ‘the
son of Abu Bekr is fallen a martyr, and Egypt hath departed from us.’
 CHAPTER XLIV.
THE REMAINDER OF ALY’S REIGN.

A.H. XXXVIII.–XL. A.D. 658–660.

No gleam of fortune lighted up the

remaining days of Aly’s reign. What with Remainder of Aly’s reign.
the rising of fanatics at home, and the
threats of the rival Caliphate abroad, his life was one continual
struggle. And, moreover, the daily exhibition of indifference and
disloyalty in Kûfa, the city of his choice, was a burden and
mortification hard to bear.
The loss of Egypt, and the cruel death
of Mohammed son of Abu Bekr, preyed Insurrection at Bussorah
upon his mind. He withdrew into the suppressed.a.d. 658.
a.h. XXXVIII.

strictest privacy. Ibn Abbâs, fearful lest his

cousin should resign the Caliphate, or do some other rash and
unadvised thing, set out from Bussorah to visit and comfort him. This
becoming known to Muâvia, he took the opportunity, during the
absence of Ibn Abbâs, to send an emissary with the view of stirring
up the disaffected elements at Bussorah. Among certain of the clans,
he was sure of finding many who, equally with himself, sought to
avenge the blood of Othmân; few were zealously attached to the
cause of Aly; the remainder were mostly Khârejites, of the theocratic
faction, now as hostile to Aly as to Muâvia himself. Abdallah, the
Syrian agent, carrying a letter to the citizens of Bussorah, was so
well received, that Ziâd, who held temporary charge of the city, was
forced to retire with the treasures and the gubernatorial pulpit into
the stronghold of a loyal clan, from whence he wrote for help to Kûfa.
Aly at once despatched a chief of influence among the Beni Rabia,
the leading tribe at Bussorah, who were by his persuasion induced to
rally round Ziâd. After severe and bloody fighting in the city, attended
by various success, the rebels were at last defeated, and driven for
refuge to a neighbouring castle. There they were surrounded, and
the castle having been set on fire, Abdallah, with seventy of his
followers, perished in the flames. The victory was decisive for the
time; but the insurrection had brought to light the alarming spread of
disaffection, and showed how precarious was Aly’s grasp upon the
Bedouin races of this factious city.
The spirit of disturbance and unrest
was not confined to Egypt and to Khârejite émeutes.
Bussorah. During the year, we read of five
or six occasions on which considerable bands of Khârejites were
impelled by their theocratic creed to go forth and raise the standard
of rebellion. One after another they met the common fate of
slaughter and dispersion. But though crushed, the frequent repetition
of such desperate enterprises, the fruit of a wild and reckless
fanaticism, had a disturbing effect on the capital and the empire at
large. The most serious of these risings
was that led by Khirrît; and it is the more Rebellion of Khirrît in
remarkable, because this chief had with his Southern Persia,
XXXXVIII. a.d. 658.
a.h.

tribe, the Beni Nâjia, fought bravely by the

side of Aly in the battles both of the Camel and Siffîn. He was now
driven, like many others, by his strong convictions to rebel. Boldly
approaching the throne, he told Aly that since he, as Caliph, had
referred a Divine issue to the arbitration of man, he could obey him
no more, neither stand up behind him in the Mosque at prayer; but
henceforth was sworn to be his enemy. Aly, with his usual patience,
said that he would argue out the matter with him, and arranged a
meeting for the purpose. But the night before the appointed day,
Khirrît stole away from the city with all his following. ‘Gone,’ said Aly,
‘to the devil; lost, like the doomed Thâmudites!’ They were pursued,
but by so small a party that they held it at bay, and in the end
effected their escape to Ahwâz and Râm Hormuz. There they raised
the Persians, Kurds, and Christian mountaineers, by the specious
and inflammatory cry that the payment of taxes to an ungodly Caliph
must be renounced. With a band of apostate Arabs, they kindled
revolt throughout the province of Fars, and put the governor to flight.
A force from Bussorah drove them to the
shores of the Indian Ocean. But luring the suppressed, and Khirrît slain.
people by delusive arguments and
promises, they still gained head; and it was not till after a bloody
battle, in which Khirrît lost his life, that the supremacy of the
Caliphate was re-established in Southern Persia. The Mussulman
prisoners in this campaign were set at
liberty on their taking afresh the oath of Christian captives.
allegiance; but the Christians, five hundred
in number, were all marched away to be sold into captivity. The
women and children, as they were torn from their protectors, wailed
with loud and bitter cries. The hearts of many were softened.
Mascala, Governor of Ardshîr, touched by the scene, took upon
himself the cost of ransoming these Christian captives, and set them
free. Aly, hearing of it, demanded from him immediate payment at a
thousand pieces for each captive; and Mascala, unable to pay down
so great a sum, fled and joined Muâvia.[556]
The defeat of the Khârejites did not at
once restore peace to Persia; for Fars and Ziâd suppresses rebellion in
Kermân threw off their allegiance, and Persia, a.h. XXXIX. a.d. 659,
expelled their governors. To quell the spreading insurrection, Aly was
happy in the selection of Ziâd, the Chancellor of Bussorah, a man,
as we have seen, of conspicuous administrative ability. He carried
with him a great court and retinue; but it was mainly by his ready tact
in setting one rebellious prince against another, and by well-
appointed promises and favours, that he succeeded in restoring
peace. Aly recognised his service by
conferring on him the government of Fars; and is appointed Governor of
and his administration there became so Fars.
famous as to recall to Persian memories the happy age of
Nushirwân. He fixed his court at Istakhr (Persepolis), and built a
castle there, in connection with which his name was remembered for
many ages following.
Though successful thus in Persia, Aly
was still subject to trouble and molestation Expeditions from Syria
against Irâc. a.h. XXXVIII-IX.
nearer home. Muâvia, relieved now from a.d. 658–9.
apprehension on the side of Egypt, began
to annoy his rival by frequent raids on Arabia and the cities beyond
the Syrian desert. The object was various—now to ravage a province
or surprise a citadel, now to exact the tithe from the Bedouin tribes,
or, again, to force upon them allegiance to the Syrian Caliphate.
Such inroads, though not always successful, inspired a sense of
insecurity; and, what was worse than that, they betrayed more
clearly than ever the lukewarmness of the people in the cause of Aly.
These would stir neither hand nor foot to repel the Syrians invading
cities so close to them even as Ain Tamr, Anbâr, and Hît. To show his
displeasure at their listlessness and
disobedience, Aly went forth himself into Safar, a.h. XXXIX. June, a.d.
the field almost unattended. On this, the 659.
men of Kûfa, partly through shame, partly lured by the promise of
increased stipends, marched to the defence of their frontier. During
the year there were eight or ten inroads of this kind from Syria.
Though eventually repelled, it was not always without loss in
prisoners, plunder, and prestige. On one occasion, however, Aly’s
commander, with a flying column, pursued the raiders back into the
heart of Syria as far as Baalbek; and thence, turning northward,
escaped by Ricca again into Irâc. On the
other hand, Muâvia, to show his contempt Muâvia visits Mosul.
for the power of Aly, made an incursion
right across the plain of Upper Mesopotamia. For some days he
remained encamped on the banks of the Tigris; and, after leisurely
inspecting Mosul, which he had never seen before, made his way
back again to Damascus unmolested.
The fortieth year of the Hegira opened
with a new grief for Aly. At the close of the Raid of Bosor on Medîna,
year preceding, as the annual pilgrimage Mecca, and Yemen. a.h. XL.
a.d. 660.
drew near, Muâvia sent Bosor, a brave but
cruel captain of his host, with three thousand men into Arabia, to
secure for him the allegiance of the sacred cities. As he drew nigh to
Medîna, Abu Ayûb, the governor, fled to Kûfa, and Bosor entered
unopposed. Proceeding to the Great Mosque, he mounted the
sacred steps of the Prophet’s pulpit, and, recalling Othmân to mind,
thus addressed the people: ‘O citizens of Medîna! The Aged Man!
Where is the aged, grey-haired man whom, but as yesterday, and in
this very place, I swore allegiance to? Verily, but for my promise to
Muâvia, who bade me stay the sword, I had not left here a soul
alive!’ Then he threatened the leading citizens with death if they
refused to acknowledge Muâvia as their Caliph; and so, fearing for
their lives, all took the oath of allegiance to the Omeyyad ruler.
Passing on to Mecca, the same scene was enacted by the imperious
envoy there, and with the same result.[557] Then he marched south
to Yemen, where he committed great atrocities upon the adherents
of Aly. The governor, Obeidallah son of
Abbâs, escaped to his cousin at Kûfa. But He slays the infant children of
two of his little children, falling into the Aly’s cousin.
tyrant’s hands, were put to death in cold blood, as well as their
Bedouin attendant, who ventured to protest against the cruel act. An
army of four thousand men was despatched in haste from Kûfa, but
too late to stop these outrages; and Bosor made good his escape to
Syria. The wretched peninsula fared no better at the hands of the
relieving army. Many of the inhabitants of Najrân were put to death,
because they belonged to the party of Othmân. The men of Mecca
were forced to recall the oath they had just taken, and again do
homage to Aly. Similarly, the citizens of Medîna swore allegiance to
Hasan, son of Aly, at the point of the sword;[558] but no sooner were
the troops gone, than Abu Horeira, of the opposite faction, resumed
his functions as leader of the daily prayers. The cruel death of his
cousin’s infant children preyed on Aly more, perhaps, than all his
other troubles put together; and he cursed Bosor in the daily service
with a new and bitter imprecation. The disconsolate mother poured
forth her sorrow in plaintive verse, some touching couplets of which
still survive.[559]
Yet another grief was in store for Aly.
He had promoted his cousins, the sons of Abdallah son of Abbâs
Abbâs, to great dignity, giving the chief retires to Mecca.
command in Yemen to one, in Mecca to another, in Medîna to a third;
while Abdallah, the eldest, held the government of Bussorah, the
second city in his Caliphate. Complaints having reached the Court of
certain irregularities in the administration of Bussorah, Aly called
upon his cousin to render an account. Scorning to answer the
demand, Abdallah threw up his office, and, carrying his treasures
with him, retired to Mecca. Aly was much mortified at this unfriendly
act; and still more so by the desertion of his own brother, Ackîl, who
went over to Muâvia.[560]
These troubles, crowding rapidly one
upon another, entirely broke the spirit of Aly, broken in spirit,
Aly. He had no longer the heart to carry on concludes truce with Muâvia.
a.h. XL. a.d. 660.
hostilities with Syria. If he might secure the
Eastern provinces in peaceful subjection to himself, it was all that he
could hope for now. Accordingly, after lengthened correspondence,
an armistice was concluded between Aly and Muâvia, by which they
agreed to lay aside their arms, respect the territory of each other,
and maintain a friendly attitude.
It is possible that a double Caliphate
thus recognised, in two separate and The double Caliphate.
independent empires, by the Rulers of the
East and of the West, might have been prolonged indefinitely, or
even handed down in perpetuity, had not the tragical event occurred
which will be narrated in the following chapter.