Applied Water Science Volume 1:

Fundamentals and Applications

Inamuddin
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Applied Water Science Volume 1
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Applied Water Science Volume 1

Fundamentals and Applications

Edited by
Inamuddin,
Mohd Imran Ahamed,
Rajender Boddula,
and
Tauseef Ahmad Rangreez
This edition first published 2021 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA
and Scrivener Publishing LLC, 100 Cummings Center, Suite 541J, Beverly, MA 01915, USA
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10 9 8 7 6 5 4 3 2 1
 Contents

Preface xix
1 Sorbent-Based Microextraction Techniques for the Analysis
of Phthalic Acid Esters in Water Samples 1
Miguel Ángel González-Curbelo, Javier González-Sálamo,
Diana A. Varela-Martínez and Javier Hernández-Borges
1.1 Introduction 2
1.2 Solid-Phase Microextraction 6
1.3 Stir Bar Sorptive Extraction 25
1.4 Solid-Phase Extraction 26
1.5 Others Minor Sorbent-Based Microextraction Techniques 48
1.6 Conclusions 52
Acknowledgements 53
References 53
2 Occurrence, Human Health Risks, and Removal of
Pharmaceuticals in Aqueous Systems: Current Knowledge
and Future Perspectives 63
Willis Gwenzi, Artwell Kanda, Concilia Danha,
Norah Muisa-Zikali and Nhamo Chaukura
2.1 Introduction 64
2.2 Occurrence and Behavior of Pharmaceutics
in Aquatic Systems 65
2.2.1 Nature and Sources 65
2.2.2 Dissemination and Occurrence in Aquatic Systems 67
2.2.3 Behaviour in Aquatic Systems 71
2.3 Human Health Risks and Their Mitigation 73
2.3.1 Human Exposure Pathways 73
2.3.2 Potential Human Health Risks 74
2.3.3 Human Health Risks: A Developing World Perspective 81
2.3.4 Removal of Pharmaceuticals 82

v
vi Contents

2.3.4.1 Conventional Removal Methods 83

2.3.4.2 Advanced Removal Methods 85
2.3.4.3 Hybrid Removal Processes 88
2.4 Knowledge Gaps and Future Research Directions 88
2.4.1 Increasing Africa’s Research Footprint 88
2.4.2 Hotspot Sources and Reservoirs 89
2.4.3 Behavior and Fate in Aquatic Systems 89
2.4.4 Ecotoxicology of Pharmaceuticals and Metabolites 89
2.4.5 Human Exposure Pathways 89
2.4.6 Human Toxicology and Epidemiology 90
2.4.7 Removal Capacity of Low-Cost Water Treatment
Processes 90
2.5 Summary, Conclusions, and Outlook 90
Author Contributions 91
References 91
3 Oil-Water Separations 103
Pallavi Jain, Sapna Raghav and Dinesh Kumar
3.1 Introduction 103
3.2 Sources and Composition 106
3.3 Common Oil-Water Separation Techniques 106
3.4 Oil-Water Separation Technologies 107
3.4.1 Advancement in the Technology of Membrane 111
3.4.1.1 Polymer-Based Membranes 111
3.4.1.2 Ceramic-Based Membranes 111
3.5 Separation of Oil/Water Utilizing Meshes 113
3.5.1 Mechanism Involved 113
3.5.2 Meshes Functionalization 114
3.5.2.1 Inorganic Materials 115
3.5.2.2 Organic Materials 115
3.6 Separation of Oil-Water Mixture Using Bioinspired Surfaces 116
3.6.1 Nature’s Lesson 116
3.6.2 Superhydrophilic/Phobic and Superoleophilic/Phobic
Porous Surfaces 117
3.7 Conclusion 118
Acknowledgment 118
References 119
4 Microplastics Pollution 125
Agnieszka Dąbrowska
4.1 Introduction and General Considerations 125
 Contents vii

4.2 Key Scientific Issues Concerning Water and

Microplastics Pollution 126
4.3 Marine Microplastics: From the Anthropogenic Litter
to the Plastisphere 131
4.4 Social and Human Perspectives: From Sustainable
Development to Civil Science 133
4.5 Conclusions and Future Projections 134
References 134
5 Chloramines Formation, Toxicity, and Monitoring Methods
in Aqueous Environments 139
Rania El-Shaheny and Mahmoud El-Maghrabey
5.1 Introduction 140
5.2 Inorganic Chloramines Formation and Toxicity 140
5.3 Analytical Methods for Inorganic Chloramines 143
5.3.1 Colorimetric and Batch Methods 144
5.3.2 Chromatographic Methods 148
5.3.3 Membrane Inlet Mass Spectrometry 150
5.4 Organic Chloramines Formation and Toxicity 151
5.5 Analytical Methods for Organic Chloramines 154
5.6 Conclusions 156
References 156
6 Clay-Based Adsorbents for the Analysis of Dye Pollutants 163
Mohammad Shahadat, Momina, Yasmin, Sunil Kumar,
Suzylawati Ismail, S. Wazed Ali and Shaikh Ziauddin Ahammad
6.1 Introduction 164
6.1.1 Biological Method 165
6.1.2 Physical Method 165
6.1.3 Why Only Clays? 165
6.1.4 Clay-Based Adsorbents 166
6.1.4.1 Kaolinite 166
6.1.4.2 Rectorite 168
6.1.4.3 Halloysite 169
6.1.4.4 Montmorillonite 170
6.1.4.5 Sepiolite 170
6.1.4.6 Laponite 171
6.1.4.7 Bentonite 171
6.1.4.8 Zeolites 172
6.2 Membrane Filtration 180
6.3 Chemical Treatment 181
viii Contents

6.3.1 Fenton and Photo-Fenton Process 182

6.3.2 Mechanism Using Acid and Base Catalyst 182
6.4 Photo-Catalytic Oxidation 186
6.5 Conclusions 188
Acknowledgments 188
References 188
7 Biochar-Supported Materials for Wastewater Treatment 199
Hanane Chakhtouna, Mohamed El Mehdi Mekhzoum,
Nadia Zari, Hanane Benzeid, Abou el kacem Qaiss
and Rachid Bouhfid
7.1 Introduction 200
7.2 Generalities of Biochar: Structure, Production,
and Properties 201
7.2.1 Biochar Structure 201
7.2.2 Biochar Production 203
7.2.2.1 Pyrolysis 204
7.2.2.2 Gasification 204
7.2.2.3 Hydrothermal Carbonization 205
7.2.3 Biochar Properties 205
7.2.3.1 Porosity 205
7.2.3.2 Surface Area 207
7.2.3.3 Surface Functional Groups 207
7.2.3.4 Cation Exchange Capacity 210
7.2.3.5 Aromaticity 210
7.3 Biochar-Supported Materials 212
7.3.1 Magnetic Biochar Composites 212
7.3.2 Nano-Metal Oxide/Hydroxide-Biochar Composites 214
7.3.3 Functional Nanoparticles-Coated Biochar
Composites 216
7.4 Conclusion 220
References 222
8 Biological Swine Wastewater Treatment 227
Aline Meireles dos Santos, Alberto Meireles dos Santos,
Patricia Arrojo da Silva, Leila Queiroz Zepka
and Eduardo Jacob-Lopes
8.1 Introduction 227
8.2 Swine Wastewater Characteristics 228
8.3 Microorganisms of Biological Swine Wastewater Treatment 231
8.4 Classification of Biological Swine Wastewater Treatment 235
 Contents ix

8.5 Biological Processes For Swine Wastewater Treatment 236

8.5.1 Suspended Growth Processes 237
8.5.1.1 Activated Sludge Process 237
8.5.1.2 Sequential Batch Reactor 237
8.5.1.3 Sequencing Batch Membrane Bioreactor 238
8.5.1.4 Anaerobic Contact Process 238
8.5.1.5 Anaerobic Digestion 238
8.5.2 Attached Growth Processes 239
8.5.2.1 Rotating Biological Contactor 239
8.5.2.2 Upflow Anaerobic Sludge Blanket 240
8.5.2.3 Anaerobic Filter 240
8.5.2.4 Hybrid Anaerobic Reactor 241
8.6 Challenges and Future Prospects in Swine Wastewater
Treatment 241
References 242
9 Determination of Heavy Metal Ions From Water 255
Ritu Payal and Tapasya Tomer
9.1 Introduction 255
9.2 Detection of Heavy Metal Ions 256
9.2.1 Atomic Absorption Spectroscopy 257
9.2.2 Nanomaterials 257
9.2.3 High-Resolution Surface Plasmon Resonance
Spectroscopy with Anodic Stripping Voltammetry 258
9.2.4 Biosensors 259
9.2.4.1 Enzyme-Based Biosensors 260
9.2.4.2 Electrochemical Sensors 261
9.2.4.3 Polymer-Based Biosensors 261
9.2.4.4 Bacterial-Based Sensors 262
9.2.4.5 Protein-Based Sensors 262
9.2.5 Attenuated Total Reflectance 262
9.2.6 High-Resolution Differential Surface Plasmon
Resonance Sensor 262
9.2.7 Hydrogels 263
9.2.8 Chelating Agents 264
9.2.9 Ionic Liquids 265
9.2.10 Polymers 266
9.2.10.1 Dendrimers 266
9.2.11 Macrocylic Compounds 266
9.2.12 Inductively Coupled Plasma Mass Spectrometry 267
x Contents

9.3 Conclusions 267

References 268
10 The Production and Role of Hydrogen-Rich Water
in Medical Applications 273
N. Jafta, S. Magagula, K. Lebelo, D. Nkokha and M.J. Mochane
10.1 Introduction 273
10.2 Functional Water 275
10.3 Reduced Water 275
10.4 Production of Hydrogen-Rich Water 277
10.5 Mechanism Hydrogen Molecules During Reactive
Oxygen Species Scavenging 279
10.6 Hydrogen-Rich Water Effects on the Human Body 280
10.6.1 Anti-Inflammatory Effects 280
10.6.2 Anti-Radiation Effects 281
10.6.3 Wound Healing Effects 282
10.6.4 Anti-Diabetic Effects 284
10.6.5 Anti-Neurodegenerative Effects 285
10.6.6 Anti-Cancer Effects 285
10.6.7 Anti-Arteriosclerosis Effects 285
10.7 Other Effects of Hydrogenated Water 285
10.7.1 Effect of Hydrogen-Rich Water
in Hemodialysis 285
10.7.2 Effect on Anti-Cancer Drug Side Effects 286
10.8 Applications of Hydrogen-Rich Water 286
10.8.1 In Health Care 286
10.8.2 In Sports Science 288
10.8.3 In Therapeutic Applications and Delayed
Progression of Diseases 289
10.9 Safety of Using Hydrogen-Rich Water 290
10.10 Concluding Remarks 291
References 292
11 Hydrosulphide Treatment 299
Marzie Fatehi and Ali Mohebbi
11.1 Introduction 300
11.1.1 Agriculture 302
11.1.2 Medical 307
11.1.3 Industrial 315
11.2 Conclusions 325
References 326
 Contents xi

12 Radionuclides: Availability, Effect, and Removal Techniques 331

Tejaswini Sahoo, Rashmirekha Tripathy, Jagannath Panda,
Madhuri Hembram, Saraswati Soren, C.K. Rath,
Sunil Kumar Sahoo and Rojalin Sahu
12.1 Introduction 332
12.1.1 Available Radionuclides in the Environment 333
12.1.1.1 Uranium 333
12.1.1.2 Thorium (Z = 90) 334
12.1.1.3 Radium (Z = 88) 335
12.1.1.4 Radon (Z = 86) 336
12.1.1.5 Polonium and Lead 336
12.1.2 Presence of Radionuclide in Drinking Water 337
12.1.2.1 Health Impacts of Radionuclides 338
12.1.2.2 Health Issues Caused Due to Uranium 338
12.1.2.3 Health Issues Caused Due to Radium 339
12.1.2.4 Health Issues Caused Due to Radon 339
12.1.2.5 Health Issues Caused Due to Lead
and Polonium 339
12.2 Existing Techniques and Materials Involved in Removal
of Radionuclide 340
12.2.1 Ion Exchange 340
12.2.2 Reverse Osmosis 340
12.2.3 Aeration 341
12.2.4 Granulated Activated Carbon 341
12.2.5 Filtration 342
12.2.6 Lime Softening, Coagulation, and Co-Precipitation 342
12.2.7 Flocculation 343
12.2.8 Nanofilteration 343
12.2.9 Greensand Filteration 344
12.2.10 Nanomaterials 344
12.2.10.1 Radionuclides Sequestration by MOFs 344
12.2.10.2 Radionuclides Removal by COFs 345
12.2.10.3 Elimination of Radionuclides by GOs 346
12.2.10.4 Radionuclide Sequestration by CNTs 346
12.2.11 Ionic Liquids 347
12.3 Summary of Various Nanomaterial and Efficiency
of Water Treating Technology 348
12.4 Management of Radioactive Waste 348
12.5 Conclusion 350
References 350
xii Contents

13 Applications of Membrane Contactors for Water Treatment 361

Ashish Kapoor, Elangovan Poonguzhali,
Nanditha Dayanandan and Sivaraman Prabhakar
13.1 Introduction 362
13.2 Characteristics of Membrane Contactors 362
13.3 Membrane Module Configurations 365
13.4 Mathematical Aspects of Membrane Contactors 366
13.5 Advantages and Limitations of Membrane Contactors 367
13.5.1 Advantages 367
13.5.1.1 High Interfacial Contact 368
13.5.1.2 Absence of Flooding and Loading 368
13.5.1.3 Minimization of Back Mixing
and Emulsification 368
13.5.1.4 Freedom for Solvent Selection 368
13.5.1.5 Reduction in Solvent Inventory 368
13.5.1.6 Modularity 369
13.5.2 Limitations 369
13.6 Membrane Contactors as Alternatives to Conventional
Unit Operations 370
13.6.1 Liquid-Liquid Extraction 370
13.6.2 Membrane Distillation 370
13.6.3 Osmotic Distillation 372
13.6.4 Membrane Crystallization 372
13.6.5 Membrane Emulsification 372
13.6.6 Supported Liquid Membranes 373
13.6.7 Membrane Bioreactors 373
13.7 Applications 374
13.7.1 Wastewater Treatment 374
13.7.2 Metal Recovery From Aqueous Streams 375
13.7.3 Desalination 375
13.7.4 Concentration of Products in Food
and Biotechnological Industries 375
13.7.5 Gaseous Stream Treatment 376
13.7.6 Energy Sector 376
13.8 Conclusions and Future Prospects 377
References 378
14 Removal of Sulfates From Wastewater 383
Ankita Dhillon, Rekha Sharma and Dinesh Kumar
14.1 Introduction 383
 Contents xiii

14.2 Effect of Sulfate Contamination on Human Health 384

14.3 Groundwater Distribution of Sulfate 384
14.4 Traditional Methods for Sulfate Removal 385
14.4.1 Treatment With Lime 385
14.4.2 Treatment With Limestone 386
14.4.3 Wetlands 387
14.5 Modern Day’s Technique for Sulfate Removal 387
14.5.1 Nanofiltration 387
14.5.2 Electrocoagulation 388
14.5.3 Precipitation Methods 389
14.5.4 Adsorption 391
14.5.5 Ion Exchange 392
14.5.6 Biological Treatment 393
14.5.7 Removal of Sulfate by Crystallization 394
14.6 Conclusions and Future Perspective 394
Acknowledgment 395
References 395
15 Risk Assessment on Human Health With Effect
of Heavy Metals 401
Athar Hussain, Manjeeta Priyadarshi, Fazil Qureshi
and Salman Ahmed
15.1 Introduction 402
15.2 Toxic Effects Heavy Metals on Human Health 403
15.3 Biomarkers and Bio-Indicators for Evaluation
of Heavy Metal Contamination 406
15.3.1 Hazard Quotient 407
15.3.2 Transfer Factor 407
15.3.3 Daily Intake of Metal 408
15.3.4 The Bioaccumulation Factor 409
15.3.5 Translocation Factor 410
15.3.6 Enrichment Factor 410
15.3.7 Metal Pollution Index 412
15.3.8 Health Risk Index 412
15.3.9 Pollution Load Index 412
15.3.10 Index of Geo-Accumulation 413
15.3.11 Potential Risk Index 413
15.3.12 Exposure Assessment 414
15.3.13 Carcinogenic Risk 415
References 417
xiv Contents

16 Water Quality Monitoring and Management: Importance,

Applications, and Analysis 421
Abhinav Srivastava and V.P. Sharma
16.1 Qualitative Analysis: An Introduction to Basic Concept 422
16.2 Significant Applications of Qualitative Analysis 422
16.2.1 Water Quality 424
16.2.2 Water Quality Index 426
16.3 Qualitative Analysis of Water 427
16.3.1 Sampling Procedure 428
16.3.2 Sample Transportation and Preservation 429
16.3.3 Some Important Physico-Chemical Parameters
of Water Quality 431
16.4 Existing Water Quality Standards 434
16.5 Quality Assurance and Quality Control 435
16.6 Conclusions 437
References 437
17 Water Quality Standards 441
Hosam M. Saleh and Amal I. Hassan
17.1 Introduction 442
17.2 Chemical Standards for Water Quality 443
17.2.1 Physical Standards 443
17.2.2 Chemical Standards for Salt Water Quality 445
17.2.3 Biological Standards 446
17.2.4 Radiation Standards 447
17.2.5 Wastewater and Water Quality 447
17.3 Inorganic Substances and Their Effect on Palatability
and Household Uses 451
17.3.1 Aluminum 451
17.3.2 Calcium 451
17.3.3 Magnesium 452
17.3.4 Chlorides 452
17.4 The Philosophy of Setting Standards for Drinking Water
(Proportions and Concentrations of Water Components) 457
17.5 Detection of Polychlorinated Biphenyls 458
17.6 The Future Development of Water Analysis 459
17.7 Conclusion 460
References 460
 Contents xv

18 Qualitative and Quantitative Analysis of Water 469

Amita Chaudhary, Ankur Dwivedi and Ashok N Bhaskarwar
18.1 Introduction 469
18.2 Sources of Water 470
18.3 Water Quality 472
18.3.1 Physical Parameters 472
18.3.2 Chemical Parameters 472
18.3.3 Biological Parameters 474
18.3.4 Water Quality Index 474
18.4 Factors Affecting the Quality of Surface Water 476
18.5 Quantitative Analysis of the Organic Content of the
Wastewater 477
18.5.1 Biochemical Oxygen Demand 477
18.5.1.1 DO Profile Curve in BOD Test 478
18.5.1.2 Significance of BOD Test 479
18.5.1.3 Nitrification in BOD Test 480
18.5.2 Chemical Oxygen Demand 480
18.5.3 Theoretical Oxygen Demand (ThOD) 482
18.6 Treatment of Wastewater 483
18.6.1 Primary Treatment Method 484
18.6.1.1 Pre-Aeration 484
18.6.1.2 Flocculation 484
18.6.2 Secondary Treatment 485
18.6.2.1 Aerobic Biological Process 485
18.6.2.2 Anaerobic Biological Treatment 485
18.6.2.3 Activated Sludge Process 487
18.6.3 Tertiary Treatment 488
18.6.3.1 Nutrients Removal 488
18.6.3.2 Phosphorus Removal 490
18.6.3.3 Ion-Exchange Process 490
18.6.3.4 Membrane Process 491
18.6.3.5 Disinfection 491
18.6.3.6 Coagulation 491
18.7 Instrumental Analysis of Wastewater Parameters 492
18.7.1 Hardness 492
18.7.2 Alkalinity 492
18.7.3 pH 493
18.7.4 Turbidity 493
xvi Contents

18.7.5 Total Dissolved Solids 494

18.7.6 Total Organic Carbon 494
18.7.7 Color 495
18.7.8 Atomic Absorption Spectroscopy 495
18.7.9 Inductive Coupled Plasma–Mass Spectroscopy 496
18.7.10 Gas Chromatography With Mass Spectroscopy 497
18.8 Methods for Qualitative Determination of Water 497
18.8.1 Weight Loss Method 497
18.8.2 Karl Fischer Method 498
18.8.3 Fourier Transform Infrared Spectroscopy
Method 499
18.8.4 Nuclear Magnetic Resonance Spectroscopy
Method 499
18.9 Conclusion 500
References 500
19 Nanofluids for Water Treatment 503
Charles Oluwaseun Adetunji, Wilson Nwankwo,
Olusola Olaleye, Olanrewaju Akinseye, Temitope Popoola
and Mohd Imran Ahamed
19.1 Introduction 504
19.2 Types of Nanofluids Used in the Treatment of Water 505
19.2.1 Zero-Valent Metal Nanoparticles 505
19.2.1.1 Silver Nanoparticles (AgNPs) 505
19.2.1.2 Iron Nanoparticles 506
19.2.1.3 Zinc Nanoparticles 507
19.2.2 Metal Oxides Nanoparticles 507
19.2.2.1 Tin Dioxide (TiO2) Nanoparticles 507
19.2.2.2 Zinc Oxide Nanoparticles (ZnO NPs) 508
19.2.2.3 Iron Oxides Nanoparticles 508
19.2.3 Carbon Nanotubes 509
19.2.4 Nanocomposite Membranes 509
19.2.5 Modes of Action of These Nanofluids 509
19.2.5.1 Carbon-Based Nano-Adsorbents (CNTs)
for Organic Expulsion 509
19.2.5.2 Heavy Metal Removal 510
19.2.5.3 Metal-Based Nano-Adsorbents 510
19.2.5.4 Polymeric Nano-Adsorbents 511
19.2.5.5 Nanofiber Membranes 511
19.2.5.6 Some Applications of Nanofluids
in the Treatment of Water 512
 Contents xvii

19.2.5.7 Informatics and AI Nanofluid-Enhanced

Water Treatment 513
19.3 Conclusion and Recommendation to Knowledge 516
References 516
Index 525
 Preface

Applied Water Science

I-Fundamentals and Applications
Inamuddin1, Mohd Imran Ahamed2, Rajender Boddula3
and Tauseef Ahmad Rangreez4
1
Department of Applied Chemistry, Zakir Husain College of Engineering and
Technology, Faculty of Engineering and Technology, Aligarh Muslim University,
Aligarh, India
2
Department of Chemistry, Faculty of Science, Aligarh Muslim University,
Aligarh, India
3
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication,
National Center for Nanoscience and Technology, Beijing, China
4
Department of Chemistry, National Institute of Technology, Srinagar,
Jammu and Kashmir, India

Water is one of the precious and basic needs of life for all living beings and
is a precious national asset. Without it, the existence of life cannot be imag-
ined. Availability of pure water is decreasing day by day, and water scarcity
has become a major problem that is faced by our society for the past few
years. Hence, it is essential to find and disseminate the key solutions for
water quality and scarcity issues. The inaccessibility and poor water qual-
ity continue to pose a major threat to human health worldwide. Around
billions of people lacking to access drinkable water. The water contains the
pathogenic impurities, which are responsible for water-borne diseases. The
concept of water quality mainly depends on the chemical, physical, biolog-
ical, and radiological measurement standards to evaluate the water quality
and determine the concentration of all components and then to compare
the results of this concentration with the purpose for which this water is

xix
xx Preface

used. Therefore, awareness and a firm grounding in water science are the
primary needs of readers, professionals, and researchers working in this
research area.
This book explores the basic concepts and applications of water sci-
ence. It provides an in-depth look at water pollutants’ classification, water
recycling, qualitative and quantitative analysis, and efficient wastewater
treatment methodologies. It also provides occurrence, human health
risk assessment, strategies for removal of radionuclides, and pharma-
ceuticals in aquatic systems. The book chapters are written by leading
researchers throughout the world. This book is an invaluable guide to
students, professors, scientists, and R&D industrial specialists working
in the field of environmental science, geoscience, water science, physics,
and chemistry.
Chapter 1 provides a general overview of different analytical method-
ologies that have been proposed for the analysis of phthalic acid esters in
water samples. Special attention has been given to methods based on the
application of sorbent-based microextraction techniques (i.e., solid-phase
microextraction and micro solid-phase extraction magnetized or not,
among others).
Chapter 2 discusses the occurrence, dissemination, and behavior of
pharmaceuticals in aquatic environments. Human exposure pathways and
health risks, including the emergence of antimicrobial resistance are sum-
marized. Risk factors promoting human exposure in developing countries
are discussed. Methods for removal of pharmaceuticals and future research
directions are also highlighted.
Chapter 3 focuses on the latest developments in the methods for the oil/
water separation through filtration of the membrane using distinct materi-
als with surface properties that are super wetting.
Chapter 4 presents the fundamental studies on the interdisciplinary
issue of microplastic-based pollution of water environments; the scientific
approach and roadmap to this complex problem are discussed.
Chapter 5 summarizes the routes of formation of organic and inorganic
chloramines upon chlorination disinfection. Chloramine’s possible health
risks to humans including mutagenicity and hemolytic anemia are dis-
cussed. Further, the analytical methods for their control in aqueous envi-
ronments are summarized. Selective methods including chromatographic
and pH-controlled colorimetric techniques are highlighted.
Chapter 6 highlights the removal of industrial dyes using different
approaches such as clay-based adsorbents, membrane filtration, and chem-
ical treatment with special focus on clay-based low-cost adsorbents. The
 Preface xxi

results of dyes’ adsorption study are discussed and compared with other
reported wastewater treatment technologies.
Chapter 7 provides a general description of biochar material from the
preparation (synthetic methods) to its application as a powerful adsor-
bent in the wastewater treatment field. Recent advancements of biochar-­
supported materials with a focus on their applications for different
contaminants’ removal and the underlying mechanisms are also discussed.
Chapter 8 focuses on biological processes for swine wastewater treat-
ment. Therefore, it details the swine wastewater characteristics, microor-
ganisms, metabolic pathways involved, and biological processes in swine
wastewater treatment. Besides, challenges and prospects in this research
field are also presented.
Chapter 9 discusses various imperative techniques to detect hazardous
metal ions in various water reservoirs. The toxicological effects of various
metal ions on living beings and atmosphere along with their detection lim-
its, in addition to future perspectives of these procedures, are highlighted.
Chapter 10 discusses the production of hydrogen-rich water and its
role in medical applications. Firstly, a concise discussion of two of the pro-
duction methods of hydrogen-rich water is provided. Lastly, the medical
benefits, medical applications, and the safety of hydrogen-rich water are
discussed in detail.
Chapter 11 focuses on the application of hydrosulfide treatment in med-
icine, agriculture, and industry fields. Hydrosulfide anion is considered as
an innovative gaseous signaling molecule and plays significant biologi-
cal roles in the organisms. Its performance is discussed in detail for the
improvement of biotic/abiotic stress tolerance of cells.
Chapter 12 discusses the properties of available radionuclides including
uranium, lead, polonium, cesium, strontium, thorium, radon, and radium.
Moreover, the health problem caused due to these radionuclides contam-
inated water is also highlighted. Techniques involved in the removal of
radionuclides including ion exchange, aeration, filtration, nanofiltration,
and flocculation are summarized.
Chapter 13 reviews the developing applications of membrane contactors
in water treatment and desalination demonstrating their ability to substi-
tute or supplement the conventional separation processes. The advantages
and limitations of membrane contactors are discussed and their potential
for value recovery from spent streams of small and medium industries are
highlighted.
Chapter 14 comprehensively reviews all the sulfate remediation tech-
nologies and also lists various methods involved in tackling the sulfate
xxii Preface

problem from wastewater. Both conventional methods and modern-day

technologies are covered in this chapter for sulfate removal.
Chapter 15 discusses the various sources and pathways of heavy met-
als’ movement and accumulation in the environment. The toxicity effects
of these heavy metals on human health are also presented. Various bio-­
indicators and biomarkers generally used for the assessment of heavy
metal-­based pollution about intake, hazard, toxicity, and transfer factor are
discussed. Also, details of various indices associated with health risk, car-
cinogenic risk, and exposure assessment are focused and recommended.
Chapter 16 emphasizes that the analysis of water is an important multi-
step process and vital for surveillance and management. The monitoring
should be a dynamic procedure with the adoption of techno-economic and
state-of-art techniques. We need to improve water quality, minimize pol-
lutants, conserve for the generations, and upgrade awareness levels. Every
drop of water counts and has the hidden story of life.
Chapter 17 deals with chemical standards for water quality and explains
the philosophy of establishing these standards. In addition to the effect
of inorganic substances on water quality, it takes into account the future
development of water analysis to make water clean and suitable for human
use.
Chapter 18 describes the different approaches used to measure water
both quantitatively and qualitatively. The dischargeable and acceptable
limits are also tabulated in this chapter as per WHO and BIS guidelines.
The simulation equations for estimating the water quality index are pre-
sented. Additionally, wastewater treatment techniques are also explained
in three stages.
Chapter 19 discusses the application of nanofluids as one of the sustain-
able bioremediation techniques for the treatment and purification of heav-
ily contaminated water. Different types of nanofluids used in the treatment
of water such as zero-valent metal nanoparticles, metal oxides nanoparti-
cles, carbon nanotubes, and nanocomposites are also highlighted.
 1
Sorbent-Based Microextraction
Techniques for the Analysis of Phthalic
Acid Esters in Water Samples
Miguel Ángel González-Curbelo1, Javier González-Sálamo2,3,
Diana A. Varela-Martínez1,2 and Javier Hernández-Borges2,3*

Departamento de Ciencias Básicas, Facultad de Ingeniería, Universidad EAN,

1

Bogotá D.C., Colombia

2
Departamento de Química, Unidad Departamental de Química Analítica,
Facultad de Ciencias, Universidad de La Laguna (ULL). Avda. Astrofísico
Fco. Sánchez, San Cristóbal de La Laguna, España
3
Instituto Universitario de Enfermedades Tropicales y Salud Pública de Canarias,
Universidad de La Laguna (ULL). Avda. Astrofísico Fco. Sánchez, San Cristóbal de
La Laguna, España

Abstract
Current society is living in a world in which it is exposed to a broad spectrum of
contaminants that can pose different risks for health. In this sense, we are daily
bombarded with news related to pollution by plastic residues (especially in the
oceans), being one of the main issues that humans must face today, not only
because of the direct effects of plastics but also because of the variety of contami-
nants they can release to the environment. Probably, the most important ones are
phthalic acid esters (PAEs), since they easily migrate from the polymeric matrix to
the surrounding media, acting as endocrine disruptors in human organisms and
resulting in multiple diseases. Their occurrence in water matrices is of especial
importance, since it is essential for life, and the presence of PAEs, even at very low
levels, can cause serious health problems. This book chapter aims at providing a
general and critical overview of the different analytical methodologies that have
been developed for the analysis of PAEs in water samples and which are based on
the application of sorbent-based microextraction techniques, which is one of the
current trends in the Analytical Chemistry field.

*Corresponding author: jhborges@ull.edu.es

Inamuddin, Mohd Imran Ahamed, Rajender Boddula, and Tauseef Ahmad Rangreez (eds.) Applied
Water Science Volume 1: Fundamentals and Applications, (1–62) © 2021 Scrivener Publishing LLC

1
2 Applied Water Science Volume 1

Keywords: Phthalic acid esters, analytical methods, sample preparation,

microextraction techniques, water samples, sorbents

1.1 Introduction
Phthalic acid esters (PAEs) are a group of dialkyl or alkylaryl esters of
phthalic acid (see Figure 1.1), commonly known as phthalates, which
are widely used as additives in the polymer industry but also added to
paints, adhesives, lubricants, and cosmetics, among others [2]. As an
example, low-molecular PAEs such as butyl benzyl phthalate (BBP),
dibutyl phthalate (DBP), and diethyl phthalate (DEP) are widely used
as solvents and emulsifiers to maintain color and fragrance mainly in
beauty products and pharmaceuticals, while high-molecular PAEs such
as di(2-ethylhexyl) phthalate (DEHP) are highly used as plasticizers to
make polymeric materials more workable and flexible. As a result of the
extremely high production of such products, especially plastics, PAEs are
exorbitantly present in the daily life. Among them, DEHP is the most
currently used. In fact, its production as plasticizer is estimated to be
a quarter of the total [3, 4]. Due to these widespread applications and
intensive production, together with the fact that they are only retained
in the polymer structure through weak secondary molecular interactions
and not covalently, PAEs can easily migrate to the environment. As a
result, PAEs have become ubiquitous contaminants in the environment,
in particular, they can be found in natural waters such as lake, river, sea,
and ground waters [5, 6], especially those adjacent or downstream from
industrial locations [5]. In addition, their possible migration to drink-
ing waters that are in contact with plastic materials like mineral and tap
waters must also be taken into account, as well as their final presence in
waste waters [5, 7].
It has already been demonstrated that many PAEs act as endocrine dis-
ruptors and that they can be toxic for reproduction, even at extremely
low concentrations [8–11]. Even more worrying is the fact that certain
PAEs can be easily degraded in the environment by bacteria and fungi
and their degradation products can also have an important toxicity. Such
is the case of DEHP that can be degraded to DBP, DEP, and especially to
mono-2-ethylhexyl phthalate (MEHP), which has shown to be more toxic
than DEHP [12, 13] (see Figure 1.2). As a result of the high human expo-
sure to PAEs and their metabolites, their potential risks for health and
their persistence, several organizations have established an increasingly
broad and restrictive legislation. As examples, the European Union has
 Phthalates Microextraction From Water 3

O
R1
O
O
R2
O

Name Abbreviations R1 Group R2 Group

Dimethyl phthalate DMP

Diethyl phthalate DEP

DMEP O O
Di(2-methoxyethyl) phthalate
Dipropyl phthalate DPP

Di(2-ethoxyethyl) phthalate DEEP O O

Benzylbutyl phthalate BBP

Dibutyl phthalate DBP

Diisobutyl phthalate DIBP

Di(2-butoxyethyl) phthalate DBEP O O

Di-n-pentyl phthalate DNPP

Diisopentyl phthalate DIPP

Dicyclohexyl phthalate DCHP

Dihexyl phthalate DHXP

Di(2-ethylhexyl) phthalate DEHP

Di-n-octyl phthalate DNOP

Diisononyl phthalate DINP

Diisodecyl phthalate DIDP

Figure 1.1 The chemical structures of PAEs. Adapted from [1]. PAEs, phthalic acid esters.

listed several PAEs as compounds suspected to produce endocrine abnor-

malities [15] and the International Agency for Research on Cancer has
classified DEHP in the group 2B (possibly carcinogenic to humans) [16].
Moreover, the US Environmental Protection Agency (EPA) has included
several PAEs (BBP, DBP, DEHP, DEP, dimethyl phthalate (DMP), and
di-n-octyl phthalate (DNOP)) in its priority list of pollutants and has
4 Applied Water Science Volume 1

O
O

O
DEHP
β-oxidation
De-esterification

β-oxidation
O

O O
O
O
OH O

MEHP O
DBP

β-oxidation

De-esterification
O
cation
terifi O
D e-es
ion O
ficat
steri
OH De - e O
DEP
O
O Trans-esterification

OH Trans-esterification
PA Trans-esterification Trans-esterification

Figure 1.2 DEHP biodegradation pathways to obtain MEHP, DBP, and DEP. Reprinted
from [14] with permission from Elsevier. DBP, dibutyl phthalate; DEHP, di-2-ethylhexyl
phthalate; DEP, diethyl phthalate; MEHP, mono-2-ethylhexyl phthalate; PA, polyacrylate.

established limits of 6 µg/L and 400 µg/L for DEHP and di(2-ethylhexyl)
adipate (DEHA) in drinking water, respectively [17], while this maximum
allowed concentration has been established in 8 µg/L for DEHP by the
World Health Organization [18] and in 1.3 µg/L in surface waters by the
European Union [19]. Considering all the above mentioned, it is clear that
there is an increasing need to develop highly sensitive and reliable analyt-
ical methods for monitoring trace amounts of PAEs in different samples
and, especially, in water.
PAEs have been analyzed in water samples using gas chromatog-
raphy (GC) coupled to flame ionization detectors (FIDs) [20], mass
 Phthalates Microextraction From Water 5

spectrometry (MS) [21] and tandem MS (MS/MS) [22], or high-

performance liquid chromatography (HPLC) coupled to diode array
detectors (DADs) [23], ultraviolet (UV) [24], and MS [25]. Among
them, GC is normally the preferred technique since most PAEs are
nonpolar and thermostable. It is important to notice that, in all these
analytical methods, it has been necessary to include previous sample
preparation steps before instrumental analysis to achieve accurate and
sensitive results. These steps consist on the isolation and pre-concen-
tration of PAEs since they can be found in water samples at extremely
low concentrations. However, since PAEs are not ionizable in water,
these samples are normally analyzed directly or after a simple filtration
without pH adjustment regardless of the sample preparation technique
used in each case [26].
In this context, special attention should be paid to the risk of sample
contamination during their analysis, which would result in false positives
and/or over-estimated concentrations. As it has already been said, PAEs
are ubiquitous contaminants and this includes their possible presence in
any laboratory since they can be found in solvents, reagents, filters, etc.
Consequently, previous washing steps using PAE-free solvents, if possible
(since most organic solvents also contain some PAEs), subsequent heating
of non-volumetric glassware at high temperatures (450–550°C) for several
hours (4–5 h), washing volumetric or any glassware material with strong
oxidizing agents, and, in some cases, even wrapping in heat-treated alumi-
num foil to avoid adsorption of PAEs from the air are carried out, among
others [27–29]. Despite all these precautions, residues of PAEs may finally
appear, and the analysis of blanks should be developed on a daily basis in
every batch of samples so that background levels can be suitably subtracted
[21, 25, 30].
Until very recently, the most widely used sample preparation methods,
also for the analysis of PAEs in water samples, have been based on the
use of liquid-liquid extraction (LLE) and solid-phase extraction (SPE) [31,
32]. The need for developing quicker, simpler, and miniaturized extraction
procedures able to maintain or even to improve the required sensitivity
of the analysis has resulted in the development of new sample prepara-
tion techniques. In this sense, microextraction techniques have gained
notoriety since the extraction is carried out using amounts of extracting
phase much smaller than the sample amount (extraction of analytes is not
always exhaustive). Microextraction techniques have inherent advantages
such as exceptionally high enrichment factors, simplicity, time saving, and
the generation of small amounts of organic solvent or reagents wastes,
without affecting reproducibility, and compatibility with most analytical
6 Applied Water Science Volume 1

instrumentation [33–36]. Among these new alternatives, sorbent-based

microextraction techniques have been widely used due to the great diver-
sity of commercially available sorbents, as well as new extraction sorbents
(in particular nanomaterials) that are constantly being proposed for their
direct use or after a previous functionalization to enhance their selectivity
[35–37].
As a result of the above-mentioned issues, the aim of this book chap-
ter is to provide a general overview of the sorbent-based microextraction
techniques applied to the analysis of PAEs in water samples, which mainly
include solid-phase microextraction (SPME), dispersive SPE (dSPE), and
magnetic dSPE (m-dSPE), among others. The extraction ability to quanti-
tatively and selectively extract these target analytes will be commented and
discussed.

1.2 Solid-Phase Microextraction

SPME has been the sorbent-based microextraction technique most used
for the analysis of PAEs in water samples (see Table 1.1) probably, among
other reasons, because it allows to reduce the risk of PAEs contamination
during sample extraction with respect to other conventional extraction
techniques. On the one hand, the absence of organic solvents and addi-
tional steps reduces PAEs background levels. On the other, water is in
many occasions a simple and clean matrix that contains few interferences,
so the direct immersion (DI) mode can be used without hardly any impair-
ment of its lifetime (except for waste waters or marine water). Moreover, in
SPME, extraction, pre-concentration and direct desorption into analytical
instruments can be easily integrated in most cases.
The first studies in which SPME was applied for PAEs extraction
from water samples dealt with the direct application of commercial fiber
coatings, including polydimethylsiloxane (PDMS), polyacrylate (PA),
PDMS-divinylbenzene (DVB), carboxen (CAR)-PDMS, and carbowax
(CW)-DVB. As examples, Cao [21] demonstrated the better performance
of PDMS-DVB fibers compared to PDMS and DVB-CAR-PDMS fibers for
the headspace (HS) SPME extraction of nine PAEs (DMP, DEP, DIBP, DBP,
BBP, DHXP, DEHA, DEHP, and DNOP) from bottled water samples, while
Polo et al. [28] found that PDMS-DVB fibers also give higher extraction
efficiency than PDMS, PA, CAR-PDMS, and CW-DVB fibers for DBP, BBP,
and DNOP, but CAR-PDMS and PA fibers show a better extraction perfor-
mance for DMP and DEP, and for DEHP, although the first one provided
better results for simultaneous analysis of the target PAEs from bottled,
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