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iwaponline.com
@IWAPublishing
ISBN: 9781789063745 (paperback)
ISBN: 9781789063752 (ebook)
ISBN: 9781789063769 (ePub)
Detection and Treatment of Emerging Contaminants in Wastewater Edited by Sartaj Ahmad Bhat, Vineet Kumar,
Fusheng Li and Pradeep Verma
Detection and Treatment of Emerging Contaminants in Wastewater addresses the critical and
pressing need for effective strategies to detect and treat emerging contaminants, thereby
mitigating risks associated with their presence in wastewater. This comprehensive book
features contributions from prominent experts in the field of wastewater, providing an
up-to-date and in-depth collection of chapters dedicated to tackling this pressing issue.
Highlights:
• The book serves as an invaluable resource for identifying, assessing, and comprehensively
addressing emerging contaminants in wastewater and/or sludges. It delves into the
assessment, mitigation, and treatment of various contaminants, including microplastics,
antibiotic-resistant genes, pharmaceuticals, personal care products and industrial chemicals.
• An exploration of the behavior of microplastics in different wastewater treatment plants and
their accumulation in sludge, shedding light on their potential impact on the environment.
• An introduction to the key mechanisms for the removal of emerging pollutants from sludge
through fungal-mediated processes, offering innovative solutions for effective treatment.
• An investigation into the fate and behavior of pharmaceutically-active compounds in
wastewater, along with their potential environmental impacts. Additionally, accurate
quantification procedures for these compounds are discussed.
• The book covers new trends in the development of greener nanomaterials, evaluating their
performance for abating emerging contaminants from wastewater.
With its comprehensive insights and diverse perspectives, this book is an essential guide
for researchers, professionals, and policymakers engaged in wastewater management and
environmental protection. The practical solutions and scientific knowledge presented herein
will contribute significantly to safeguarding our water resources and ensuring a cleaner and
healthier future.
Detection and
Treatment of Emerging
Contaminants
in Wastewater
Edited by Sartaj Ahmad Bhat, Vineet Kumar,
Fusheng Li and Pradeep Verma
Detection and Treatment_layout_1.0.indd 1Detection and Treatment_layout_1.0.indd 1 26/01/2024 12:4826/01/2024 12:48
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Detection and Treatment
ofEmerging Contaminants
inWastewater
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Edited by
Sartaj Ahmad Bhat, Vineet Kumar,
FushengLiandPradeep Verma
Detection and Treatment
ofEmerging Contaminants
inWastewater
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Published by IWA Publishing
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First published 2024
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The information provided and the opinions given in this publication are not necessarily those of IWA and should
not be acted upon without independent consideration and professional advice. IWA and the Editors and Authors
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any material contained in this publication.
British Library Cataloguing in Publication Data
A CIP catalogue record for this book is available from the British Library
ISBN: 9781789063745 (paperback)
ISBN: 9781789063752 (eBook)
ISBN: 9781789063769 (ePub)
Doi: 10.2166/9781789063752
This eBook was made Open Access in April 2024.
© 2024 IWAP
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BY-NC-ND 4.0), which permits copying and redistribution for non-commercial purposes with no derivatives,
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The Editors .................................................................xiii
Prefac e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv
Chapter 1
Fate and behavior of microplastics inwastewater, accumulation in organisms
and effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Agata Egea-Corbacho, Ana Amelia Franco, Ana Pilar Martín-García,
JoséMaríaQuirogaand María Dolores Coello
1.1 Introduction .....................................................................1
1.2 Microplastics in Wastewater Treatment Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.1 Arrival of MPs at WWTPs: sources ...........................................3
1.2.2 Presence and removal of MPs in wastewater treatment units .....................3
1.2.3 Presence and accumulation of MPs in sewage sludge ............................4
1.3 Circular Economy, Regenerated Water, and Sludge as Soil Amendment:
Environmental Issues .............................................................8
1.4 Accumulation of Microplastics in Organisms and Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References...........................................................................14
Chapter 2
Occurrence and detection of pharmaceuticals in wastewater and its
subsequenttreatmentusing constructed wetlands, bioelectrochemical systems and
theircombination ............................................................ 19
Mahak Jain, Abhradeep Majumder, Pubali Mandal, Shalini Singh,
ParthaSarathiGhosaland Manoj Kumar Yadav
2.1 Introduction ....................................................................19
2.2 Types of Phacs Detected in Wastewater and their PhysicochemicalProperties ............22
Contents
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vi Detection and Treatment of Emerging Contaminants in Wastewater
2.3 Environmental Impact of the Presence of Phacs in Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.4 Challenges in Detecting Phacs in Wastewater and Strategies for their Effective Analysis 24
2.5 Challenges in Removing Phacs from Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.6 Performance of CW in Removing Phacs .............................................26
2.7 Performance of BES in Removing Phacs ............................................26
2.8 Performance of Hybrid CW–BES System in Removing Phacs ...........................28
2.9 Summary.......................................................................29
References...........................................................................30
Chapter 3
Emerging contaminants in municipal sewage/sludge: occurrence, risk assessment,
andtreatment technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Bing Wang, Tao Jiang, Nana Wang and Qianqian Zou
3.1 Introduction ....................................................................35
3.2 Occurrence of ECs in Municipal Sewage/Sludge......................................36
3.3 Risk Assessment of ECs in Municipal Sewage/Sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.3.1 Ecological risk assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.3.2 Health risk assessment ....................................................41
3.4 Treatment Technologies of ECs in Municipal Sewage/Sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.4.1 Treatment technologies of ECs in municipal sewage ............................42
3.4.1.1 Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.4.1.2 Biological treatment...............................................43
3.4.1.3 Advanced oxidation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.4.1.4 Membrane treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.4.2 Treatment technologies of ECs in municipal sludge ............................46
3.4.2.1 Aerobic composting ...............................................46
3.4.2.2 Anaerobic digestion ...............................................47
3.4.2.3 Advanced oxidation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.4.2.4 Other treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.5 Conclusion and Future Perspectives ................................................49
References...........................................................................50
Chapter 4
Recent advances in treatment of microplastics in wastewater . . . . . . . . . . . . . . . . . . . . . . . . 55
Surya Singh
4.1 Introduction ....................................................................55
4.2 Challenges in the Microplastics Removal ............................................56
4.3 Overview of Conventional Treatment Techniques and Shortcomings ....................57
4.4 Advanced Techniques for Removal of Microplastics ...................................58
4.4.1 Physical techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.4.1.1 Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.4.1.2 Filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.4.1.3 Agglomeration and sol–gel process using bioinspired molecules ..........62
4.4.1.4 Micromotors .....................................................63
4.4.2 Chemical techniques ......................................................63
4.4.2.1 Metal organic framework (MOF)-based moieties .......................63
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viiContents
4.4.2.2 Advanced oxidation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.4.3 Biological techniques......................................................64
4.4.3.1 Algal degradation .................................................64
4.4.3.2 Fungal degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.4.3.3 Bacterial degradation..............................................65
4.4.3.4 Constructed wetlands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.4.4 Miscellaneous techniques ..................................................66
4.4.4.1 Electrochemical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4.4.4.2 Nanotechnological methods ........................................66
4.4.4.3 Combinatorial methods ............................................66
4.5 Future Perspectives ..............................................................66
4.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
References...........................................................................67
Chapter 5
A brief account of the antibiotics and antibiotic resistance genes in an
aquatic environment.......................................................... 73
Nikita Yadav, Ashootosh Mandpe and Sudeep Shukla
5.1 Introduction ....................................................................73
5.1.1 Antibiotics as emerging pollutants...........................................74
5.1.2 Occurrence of antibiotics and ARGs in water bodies ...........................76
5.1.3 Global distribution of antibiotics as emerging pollutants ........................79
5.1.4 Studies for antibiotic distribution in Indian aquatic bodies . . . . . . . . . . . . . . . . . . . . . . 80
5.2 Trends in Consumption of Antibiotic Pollutants ......................................81
5.2.1 Antibiotic consumption trend at the global level ...............................81
5.2.2 Antibiotic consumption trend in India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5.3 Ecological Risk Posed by Antibiotics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5.4 Assessment and Remediation Methodologies.........................................83
5.4.1 Conventional treatment processes ...........................................84
5.4.1.1 Activated sludge process (ASP)......................................84
5.4.1.2 Membrane biological reactor (MBR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
5.4.2 Advanced emerging treatment techniques ....................................84
5.4.2.1 Ozonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
5.4.2.2 UV irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
5.4.2.3 Adsorption-based removal..........................................85
5.5 Regulations by Global Authorities for Antibiotics Utilization ...........................86
5.6 Current Advances and Future Outlook..............................................87
5.7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
References...........................................................................88
Chapter 6
Function of nanomaterials in the treatment of emerging pollutants inwastewater ....... 93
Paramjeet Dhull, Neha Saini, Mohd Aamir, Shama Parveen and Samina Husain
6.1 Introduction ....................................................................94
6.2 Classification of Nanomaterials (NMS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
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viii Detection and Treatment of Emerging Contaminants in Wastewater
6.2.1 Carbon-based nanomaterial ................................................97
6.2.1.1 Fullerene ........................................................97
6.2.1.2 Carbon nanotubes ................................................97
6.2.1.3 Graphene ........................................................98
6.2.2 Metal/metal oxide-based nanomaterials ......................................98
6.3 Synthesis and Characterization of Nanomaterials ....................................98
6.3.1 Green synthesis of nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
6.3.2 Characterization of nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.4 Nanomaterials-Based Approaches of Wastewater Treatment (WWT) ....................99
6.5 Advances in Terms of Green Approach for the Large-Scale use of Nanomaterials
inWastewater Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
6.5.1 Nanofiltration...........................................................104
6.5.2 Nano adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
6.5.3 Photocatalysis...........................................................106
6.5.4 Nano sensors ...........................................................106
6.6 Barriers Associated and Environmental Concerns of Nanotechnologies.................107
6.7 Future Perspectives of Nanomaterials in Wastewater Treatment (WWT) . . . . . . . . . . . . . . . . 108
6.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
References..........................................................................109
Chapter 7
Treatment approaches for emerging contaminants in sludge and wastewater .......... 113
Rayane Kunert Langbehn, Felipe Matheus Müller, Elisângela Edila Schneider,
Camila Pereira Senna, Eric Sanches-Simões, Júlia Pedó Gutkoski, Maikon Kelbert,
Camila Michels and HugoMoreira Soares
7.1 Introduction ...................................................................113
7.2 Biological Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
7.2.1 Conventional ...........................................................118
7.2.1.1 Activated sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
7.2.1.2 Membrane bioreactor.............................................118
7.2.1.3 Anaerobic digestion ..............................................119
7.2.1.4 Nitrogen removal ................................................119
7.2.2 Non-conventional .......................................................120
7.2.2.1 Constructed wetlands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
7.2.2.2 Composting.....................................................121
7.2.2.3 Microalgae-mediated processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
7.2.2.4 Mycoremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
7.2.2.5 Enzymatic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
7.2.2.6 Bioelectrochemical systems .......................................123
7.3 Physicochemical Processes.......................................................124
7.3.1 Advanced oxidation processes .............................................124
7.3.2 Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
7.3.3 Membrane filtration......................................................126
7.3.4 Pyrolysis ...............................................................127
7.4 Treatment Trends for ECS Removal ...............................................127
References..........................................................................129
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ixContents
Chapter 8
Novel approaches for removing emerging contaminants from sludge using
fungal-mediatedprocesses .................................................... 135
Lamia Yakkou, Sofia Houida, Maryam Chelkha, Imane Sarroukh,
SartajAhmadBhat,Rabha Abdelwahd, Mohammed Ibriz, Mohammed Raouane,
SouadAmghar and AbdellatifEl Harti
8.1 Introduction ...................................................................135
8.2 Fungal Species Used for the Removal of ECs ........................................136
8.2.1 Fungal species used for the removal of ECs from sludge........................136
8.2.2 Mechanisms by which fungi can remove ECs from sludge ......................139
8.3 Recent Advances in Fungal-Mediated Processes for EC Removal .......................142
8.3.1 Fungal reactors..........................................................143
8.3.2 Coculture-based approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
8.3.3 Enzymes application-based approach .......................................145
8.3.4 Genetically modified fungi application-based approach ........................146
8.4 Factors Affecting Fungal-Mediated Processes .......................................148
8.5 Applications of Fungal-Mediated Technology for EC Removal . . . . . . . . . . . . . . . . . . . . . . . . . 149
References..........................................................................151
Chapter 9
Tracing the pathways: the journey of emerging contaminants from wastewater
intotheenvironment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
Purusottam Tripathy, Charu Juneja, Abhishek Sharma, Om Prakash
and Sukdeb Pal
9.1 Background ...................................................................159
9.2 Emerging (Micro)Pollutants in the Environment.....................................161
9.2.1 Pharmaceuticals.........................................................161
9.2.2 Antidepressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
9.2.3 Personal care products (PCPs).............................................162
9.2.4 Polycyclic aromatic hydrocarbons (PAHs) ...................................163
9.2.5 Phthalate esters (PAEs) ...................................................163
9.2.6 Pesticides...............................................................164
9.2.7 Endocrine active compounds ..............................................164
9.2.8 Surfactants and food additives.............................................164
9.2.9 Musks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
9.3 EC in an Aqueous Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
9.3.1 Classification and sources of EC ...........................................165
9.3.2 Occurrence of EC in different water matrix ..................................165
9.3.2.1 Surface water ...................................................168
9.3.2.2 Groundwater....................................................168
9.3.2.3 Drinking water..................................................168
9.3.2.4 Wastewaters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
9.3.2.5 Other matrix ....................................................169
9.3.3 Pathways of ECs.........................................................169
9.4 Global Occurrence of Some Important ECs.........................................170
9.5 Fate of ECs in Environmental Waters ..............................................171
9.5.1 Human metabolites ......................................................171
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xDetection and Treatment of Emerging Contaminants in Wastewater
9.5.2 Microbial transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
9.5.3 Physicochemical processes ................................................172
9.6 Environmental Monitoring of ECs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
9.6.1 Sampling mode and strategy...............................................173
9.6.2 Analysis methods ........................................................173
9.7 Policy and Legislation (India) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
9.8 Conclusions and Future Outlook..................................................175
Acknowledgments ...................................................................175
References..........................................................................175
Chapter 10
Fate and behaviour of pharmaceutical and personal care products in wastewater ....... 181
Akanksha Bakshi, Megha Latwal, Sonali, Nitika Sharma, Anamika Sharma,
JatinderKaur Katnoria and Avinash Kaur Nagpal
10.1 Introduction ...................................................................181
10.2 Major Categories of PPCPs .......................................................183
10.2.1 Categories of pharmaceutical products......................................183
10.2.2 Categories of personal care products (PCPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
10.3 Occurrence of PPCPs in Water Ecosystem..........................................187
10.4 Sources and Fate of PPCPs .......................................................189
10.4.1 Sources of PPCPs in wastewater ...........................................189
10.4.2 Fate of PPCPs in wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
10.5 Harmful Effects of PPCPs........................................................189
10.6 Removal and Management of PPCPs from Wastewater ...............................191
10.6.1 Different methods of management..........................................191
10.6.1.1 Conventional systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
10.6.1.2 Membrane filtration ..............................................192
10.6.1.3 Membrane bioreactors (MBRs).....................................192
10.6.1.4 Activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
10.6.1.5 Advanced oxidation processes (AOPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
10.6.1.6 Constructed wetlands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
10.7 Conclusion and Future Prospectives ...............................................194
References..........................................................................195
Chapter 11
A review of occurrence of emerging contaminants and the advanced analytical
techniquesused for detection and removal of these pollutants in wastewater ........... 203
Masixole Sihlahla and Sihle Mngadi
11.1 Introduction ...................................................................204
11.1.1 Review methodology .....................................................207
11.2 Occurrence....................................................................207
11.3 Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
11.4 Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
11.4.1 Physiochemical methods ..................................................211
11.4.1.1 Adsorption methods..............................................212
11.4.1.2 Membrane technology ............................................213
11.4.2 Biological methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
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xiContents
11.4.3 Chemical treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
11.4.3.1 Conventional oxidation methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
11.4.3.2 Advance oxidation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
11.4.4 Emerging and hybrid treatment technology ..................................217
11.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
11.6 Future Perspective ..............................................................220
References..........................................................................221
Chapter 12
Abatement of pharmaceutical compounds in wastewater using green
nanomaterials: an eco-friendly alternative to conventional nanomaterials ............ 227
Akshay Botle, Sayli Salgaonkar, Gayatri Barabde and Mihir Herlekar
12.1 Introduction to Emerging Contaminants in Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
12.1.1 Background and significance of the topic ....................................228
12.1.2 Objectives of the study ...................................................231
12.2 Pharmaceutical Compounds in Wastewater.........................................231
12.2.1 Sources, composition, types, and toxicology of pharmaceutical compounds
inwastewater ...........................................................231
12.2.2 Impact of pharmaceutical compounds on human health and the environment.....233
12.2.3 Conventional methods for treating pharmaceutical compounds in wastewater . . . . 233
12.2.4 Limitations of conventional methods .......................................234
12.3 Nanomaterials for Wastewater Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
12.3.1 Types of nanomaterials ...................................................235
12.3.1.1 Carbon nanotubes ...............................................235
12.3.1.2 Graphene.......................................................235
12.3.1.3 Carbon and graphene dots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .236
12.3.1.4 Zero-valent metals nanoparticles ...................................236
12.3.1.5 Metal oxide nanoparticles.........................................236
12.3.2 Applications of nanomaterials in wastewater treatment ........................237
12.3.3 Advantages and disadvantages of nanomaterials..............................237
12.4 Green Nanomaterials for Wastewater Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
12.4.1 Definition and characteristics of green nanomaterials .........................238
12.4.2 Types of green nanomaterials ..............................................238
12.4.2.1 Synthesis of green nanomaterials...................................238
12.4.2.2 Plant and plant extract ...........................................238
12.4.2.3 Microorganisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
12.4.2.4 Fungi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
12.4.2.5 Algae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
12.4.3 Advantages of green nanomaterials over conventional nanomaterials ............239
12.4.4 Recent research on green nanomaterials for wastewater treatment . . . . . . . . . . . . . . 239
12.5 Abatement of Pharmaceutical Compounds in Wastewater Using Green Nanomaterials ....240
12.5.1 Mechanisms of abatement using green nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . 240
12.5.2 Factors affecting the efficiency of green nanomaterials in abating
pharmaceuticalcompounds ...............................................240
12.5.3 Comparison of the effectiveness of green over conventional nanomaterials
inabatingpharmaceutical compounds ......................................241
12.5.4 Future prospects and challenges of using green nanomaterials for abating
pharmaceutical compounds ...............................................242
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xii Detection and Treatment of Emerging Contaminants in Wastewater
12.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
12.6.1 Recommendations for future research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
12.6.2 Final thoughts and implications for practice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
12.6.3 Summary of the study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
References..........................................................................243
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Sartaj Ahmad Bhat works as a JSPS postdoctoral researcher at the River
Basin Research Center, Gifu University, Japan. He received his PhD in
environmental sciences from Guru Nanak Dev University, Amritsar,
India in 2017. His research interests focus on the vermicomposting
treatment of various solid wastes, especially for investigations on the fate
and behavior of emerging pollutants during the biological treatment of
organic wastes. He has published more than 65 papers in peer-reviewed
journals and edited over 15 books published by Elsevier, Springer, CRC
Press, IWA, and RSC. Dr Bhat serves as an associate/academic editor and
editorial board member/advisory board member of more than 15 journals
published by Frontiers, Springer, Elsevier, PLOS, Wiley, Hindawi, and
De Gruyter. Dr Bhat is a recipient of several prestigious awards such
as the JSPS Postdoctoral Fellowship to pursue research at River Basin
Research Center, Gifu University, Japan, the Basic Scientific Research Fellowship (BSR JRF, SRF) by
the University Grants Commission (UGC) India, the DST-SERB National Postdoctoral Fellowship at
CSIR-NEERI, Nagpur, India, and Swachhta Saarthi Fellowship by the Government of India. He has
also received the 2020 Outstanding Reviewer Award by the International Journal of Environmental
Research and Public Health, MDPI, and Top Peer Reviewer 2019 award in Environment and Ecology
by Web of Science and has more than 750 Verified Reviews and 70 Editor Records to his credit.
Vineet Kumar works as a national postdoctoral fellow in the Department
of Microbiology, School of Life Sciences at the Central University of
Rajasthan, Rajasthan, India. He received his MSc (2008) and MPhil (2012)
in microbiology from the Department of Microbiology at Ch. Charan
Singh University, Meerut, India. Subsequently, he earned his PhD (2018)
in environmental microbiology from Babasaheb Bhimrao Ambedkar (A
Central) University, Lucknow, India. Dr Kumar’s research work mainly
focuses on wastewater treatment and solid waste management. He has
published more than 50 articles in peer-reviewed international journals of
repute, 24 books, and 52 book chapters, on various aspects of science and
engineering, with more than 2500 citations, and h-index 30. Dr Kumar
has served as a guest editor and reviewer on more than 65 prestigious
The Editors
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xiv Detection and Treatment of Emerging Contaminants in Wastewater
International Journals, and on the editorial board of various reputed journals. He has presented several
papers relevant to his research areas at national and international conferences. He is also a recipient
of various prestigious fellowships and awards, such as the Young Scientist Award, the Rajiv Gandhi
National Fellowship by University Grants Commission (UGC), and National Postdoctoral Fellowship
by the Science and Engineering Research Board (SERB), Government of India. He is an active member
of numerous scientific societies including the Microbiology Society (UK), the Indian Science Congress
Association (India), the Association of Microbiologists of India (India), etc. He is the founder of the
Society for Green Environment, India (website: www.sgeindia.org).
Fusheng Li is a professor in the Division of Water System Safety and
Security Studies and the Graduate School of Engineering at Gifu
University, Japan. He received his BS in environmental engineering
from Lanzhou Jiaotong University of China in 1986, an MS from Kitami
Institute of Technology of Japan in 1994, and a PhD from the Gifu
University of Japan in 1998. Dr Li is directing the Division of Water
Quality Studies that covers the fields from water quality to water and
wastewater treatment, and recently to resource and energy recovery
from organic waste. The ongoing research projects in his lab include
adsorption; membrane filtration, enhanced coagulation, disinfection;
biological water and wastewater treatment; vermicomposting
treatment of vegetable waste and activated sludge; microbial fuel cell;
physicochemical water quality assessment; and biological water quality
assessment. He has over 350 scholarly publications, including more than 200 in peer-reviewed journal
papers. As principal supervisor, he has already guided 50 masters and 21 doctorate graduate students
to the completion of their degrees. Dr Li is the recipient of awards from several academic societies and
associations for his research work on water treatment and water quality dynamics studies.
Prade ep Ve rma works as a professor in the Department of Microbiology,
School of Life Sciences at Central University of Rajasthan, Rajasthan,
India. He is a well-rounded researcher with more than 21 years of
exper ience in leadi ng, super visin g, and under takin g research i n the broader
field of bioprocess and bioenergy production from lignocellulosic waste
with a focus on waste management. He earned his PhD in microbiology
from Sardar Patel University, Gujarat, India in 2002. His research area
of expertise involves microbial diversity, bioremediation, bioprocess
development, lignocellulosic, and algal biomass-based biorefinery. He has
more than 74 research articles in peer-reviewed international journals and
contributed to 46 book chapters in different edited books with citations
of more than 6000, and an h-index of 40. He has also edited four books
by international publishers such as Springer, Taylor and Francis CRC
Press, and Elsevier. He also holds 12 International patents in the field of microwave-assisted biomass
pretreatment and bio-butanol production. He is a guest editor to several journals such as Biomass
Conversion and Biorefinery (Springer), Frontier in Nanotechnology (Frontiers), and International
Journal of Environmental Research and Public Health (MDPI). He is also an editorial board member
for the Journal of Current Nanomedicine (Bentham Sciences). He is acting as a reviewer for more than
40 journals in different publication houses such as Springer, Elsevier, RSC, ACS, Nature, Frontiers,
MDPI, etc. He is also a recipient of various prestigious fellowships and awards, such as the JSPS Post-
Doctoral Fellowship and the Ron Cockcroft Award by the Swedish Society, UNESCO Fellow ASCR
Prague. He has been awarded with Fellow of Mycological Society of India (MSI-2020), Prof. P.C. Jain
Memorial Award, Mycological Society of India 2020 and Fellow of Biotech Research Society, India
(2021). He is a member of various national and international societies/academies.
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Preface
It is with great pleasure and enthusiasm that we present this comprehensive book, Detection and
Treatment of Emerging Contaminants in Wastewater, which delves into the critical challenges posed
by emerging contaminants in wastewater and explores innovative detection and treatment methods.
Wastewater management has always been a matter of paramount importance for the preservation
of our green environment and the well-being of society. However, with the rampant advancements
in industrial and technological sectors, new contaminants have emerged, presenting unprecedented
challenges for conventional wastewater treatment processes. Emerging contaminants, such as micro-
and macro plastics, pharmaceuticals, personal care products, pesticides, and industrial chemicals,
possess the potential to adversely impact on aquatic ecosystems and human health.
Sustainable domestic and industrial wastewater treatment with emerging contaminants is very
challenging for several reasons, including recyclability and scalability issues. Considering the need for
sustainable wastewater treatment, this book will be a timely contribution that will be extremely useful
in identifying and comprehensively addressing the assessment, mitigation, and treatment of emerging
contaminants in wastewater and/or sludges.
This book aims to address the urgent need for effective detection and treatment strategies to mitigate
the risks associated with emerging contaminants in wastewater. It brings together a multidisciplinary
approach, combining the expertise of researchers and practitioners from various fields, including
environmental engineering, chemistry, toxicology, and public health. Their collective knowledge
and experiences have been harnessed to create a comprehensive compilation of the latest research
findings, methodologies, and technological advancements in the field.
This book presents an up-to-date and comprehensive collection of chapters contributed by
prominent experts in the field of wastewater working in the top institutions globally. It promotes
the development of green and eco-friendly technologies for removing emerging contaminants in
wastewater treatment plants. It also highlights the need for collaboration among researchers, industry
stakeholders, and policymakers to develop robust regulations and guidelines that foster sustainable
and efficient wastewater management practices.
The 12 chapters cover the different aspects of the detection and treatment of emerging
contaminants, such as microplastics, antibiotics and antibiotic resistance genes, and pharmaceuticals
doi: 10.2166/9781789063752_xv
© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
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xvi Detection and Treatment of Emerging Contaminants in Wastewater
and personal care products in water and wastewater. The initial chapters provide an overview of
emerging contaminants, their sources, fate in the environment, and associated risks. Subsequent
sections delve into the various analytical techniques employed for detection and monitoring, including
chromatographic and spectroscopic methods, biosensors, and molecular techniques. Furthermore,
the book explores advanced treatment processes, such as membrane filtration, advanced oxidation
processes, and biological treatment, specifically tailored to address the challenges posed by emerging
contaminants.
Chapter 1 discusses the behavior of microplastics in different wastewater treatment plant units,
as well as their accumulation in the sludge. The chapter also examines the impact of microplastics
on fauna when they enter the environment. Chapter 2 discusses the occurrence of pharmaceutically
active compounds in wastewater, their potential environmental impacts, and the necessary
procedures for accurately quantifying these compounds. The chapter also addresses the possibilities
of using constructed wetlands and bioelectrochemical systems as sustainable methods for eliminating
pharmaceutically active compounds from wastewater. Chapter 3 focuses on the main occurrence
of emerging contaminants in municipal wastewater and sludge. The chapter also discusses various
treatment technologies, including anaerobic digestion, aerobic composting, and advanced oxidation,
for dealing with different types of emerging contaminants. Chapter 4 discusses recent technological
advances in the removal of microplastics from wastewater. Chapter 5 reviews the global distribution of
antibiotics in the aquatic environment, their effects on the microbial community, and the assessment
of antibiotic risks. Chapter 6 covers various types of nanomaterials and nanotechnologies that are
useful in wastewater treatment for remediating emerging pollutants in the environment. Chapter 7
discusses the biological and physicochemical processes used to remove emerging contaminants from
wastewater and sludge. Chapter 8 covers the mechanisms by which fungi remove emerging pollutants
from sludge, including biosorption, biodegradation, and enzyme production. Chapter 9 provides a
brief overview of emerging contaminants, their main categories, occurrences, points of discharge,
and toxicity in natural and engineered systems. Chapter 10 focuses on the sources, types, effects,
monitoring, and suitable removal techniques for different pharmaceuticals and personal care products
in wastewater treatment systems. Chapter 11 summarizes emerging contaminants in wastewater, their
occurrence, detection, and removal efficiency using advanced analytical techniques. Finally, Chapter
12 covers new trends in the development of greener nanomaterials and evaluates their performance
for the abatement of pharmaceutical compounds from wastewater.
We express our heartfelt gratitude to all the authors who have contributed their expertise and
valuable insights to this book. Their dedication and commitment have made this endeavor possible.
We also extend our appreciation to the International Water Association (IWA) Publishing, United
Kingdom for their support and belief in the significance of this book.
Finally, we hope that this book serves as a comprehensive reference for researchers, professionals,
and students who are passionate about advancing the field of wastewater management and ensuring
a sustainable future. Together, let us embark on a journey to detect, understand, and effectively
treat emerging contaminants in wastewater, thereby safeguarding our precious water resources and
promoting a healthier environment for generations to come.
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© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0001
Agata Egea-Corbacho1,2*, Ana Amelia Franco1, Ana Pilar Martín-García1, José María Quiroga1
and María Dolores Coello1
1Department of Environmental Technologies, Faculty of Marine and Environmental Sciences, INMAR-Marine Research
Institute,CEIMAR International Campus of Excellence of the Sea, University of Cadiz, Campus Univer sitario de Puerto Real,
11510Cádiz, Spain
2Materials and Sustainability Group, Department of Engineering, Universidad Loyola Andalucía, Avda, de las Univer sidades
s/n,41704 Dos Hermanas, Seville, Spain
*Corresponding author: agata.egea@uca.es
ABSTRACT
Studies on how microplastics (MPs) behave in wastewater treatment plants (WW TPs) are increasing day by day.
Although conventional W WTPs can efficiently remove MPs (64–99%), when considering the daily discharge rate, this
percentage would not be suf ficient. The total amount of MPs would still be discharged daily into the environment;
therefore, the final effluent can act as one of the main routes of entry of MPs into aquatic environments. This chapter
reviews the behavior of MPs in the different WWTP units, as well as their accumulation in the sludge. Subsequently,
a discussion on how the MPs from the WWTP can reach the receiving media, such as aquatic or terrestrial media
(water line and sludge line), to finally discuss how the fauna is affected by the entr y of the MPs into the environment.
These MPs can be ingested by aquatic life forms, leading to their bioaccumulation and biomagnification along the
food chain, and causing negative effects on tissues, organs, and metabolism. MPs can also act as transport vehicles
for other emerging pollutants such as pharmaceuticals and pesticides, increasing their hazardousness.
Keywords: microplastics, wastewater, sludge, biota, bioaccumulation, biotoxicity
1.1 INTRODUCTION
Plastics are synthetic polymeric materials widely used in our daily life, and due to their main
characteristics, low weight, flexibility, low cost, high plasticity, and above all durability, the global
consumption of plastics has increased especially in recent decades (Andrady, 2011). The use,
management, and disposal of plastics has become one of the issues of greatest concern worldwide in
recent years. The extensive use of this material for a multitude of applications such as construction
(16%), the textile industry (9%), the manufacture of consumer household products (10%), or packaging
Chapter 1
Fate and behavior of microplastics
inwastewater, accumulation in
organisms and effects
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2Detection and Treatment of Emerging Contaminants in Wastewater
(31%), among others, has generated a high demand and production of plastics (Organisation for
Economic Co-operation and Development [OECD], 2022). The characteristics of many of the products
currently manufactured mean that they are used only once or for a very short time (single-use plastics),
generating large amounts of waste that, in many cases, end up in landfills due to the impossibility of
reusing or recycling them.
The OECD estimates that by 2060 the use of plastics such as high-density polyethylene (HDPE)
and low-density polyethylene (LDPE), polyethylene terephthalate (PET), polypropylene (PP),
or polystyrene (PS) will be more than double from 246 to 616 Mt. These polymers alone already
account for 50% of all plastics used worldwide. According to a new OECD report (OECD, 2022),
the world generates twice as much plastic waste as it did two decades ago, with most of it ending up
in landfills, incineration, or leaking into the environment, with only 9% being successfully recycled.
Accumulation of plastic waste in aquatic ecosystems is a well-known problem. The United Nations
Environment Programme (UNEP) estimates that the world’s oceans by 2025 will have accumulated
between 100and 250 million tons of plastic debris (Alimba & Faggio, 2019; UNEP, 2014).
By 2060, in regions such as the USA and Europe, both the use and consumption of plastics and the
amount of plastic waste generated will have doubled. Currently, it is estimated that in these regions
of the planet, some 305 Mt of plastics end up in natural aquatic ecosystems, with the consequent
threat that this implies for life (OECD, 2022). These wastes reach the environment, where they can
remain for several decades to hundreds of years because they are very stable and resistant materials.
Larger plastics can fragment due to the action of natural factors such as wind, solar radiation, or tidal
movement, which produce mechanical degradation and generate smaller plastic particles (Martín-
García etal., 2023). Particles ranging in size from 1 µm to 5 mm are known as microplastics (MPs) and
have attracted the attention of the scientific community in recent years due to their high persistence
in the environment, the difficulty of elimination, and the effects they can have on living organisms,
which can even enter the trophic chain.
According to Waldschläger etal. (2020), MP enters the environment through various pathways,
such as surface runoff, wind and rain, or effluent from wastewater treatment plants (WWTP). Sources
of these micropollutants are plastic production activities, the construction industry, sports fields,
landfills, car tires, garbage, cosmetics, washing wastewater, or fishing gear losses. As mentioned above,
wastewater treatment plants are the route through which MP enters the environment, it is known
that one of the largest sources of microplastics entering the environment comes from wastewater
treatment plants (WWTPs) (Pittura et al ., 2021; Tur a n et a l., 2021). These systems are capable of
removing organic matter and large plastic particles. However, they cannot remove particles smaller
than 100 µm, and their influent and effluent tend to contain similar amounts of these smaller particles
(Freeman etal., 2020).
Although WWTPs are not designed to treat and remove MP, several authors have reported that
conventional wastewater treatment methods can remove 79–99% of the MP present in the water
line (Nandakumar etal., 2022). However, the reality is that this fraction is not removed as such but
is removed from the liquid phase but accumulates in the solid fraction of the wastewater, the sludge
(Franco et al., 2023). The current approach is a circular economy based on the reuse of maximum
products without the need to extract new raw materials. WWTPs play a very important role in this
way, as both water and sludge are reused. This reduction of waste and pollution is also carried out
to achieve sustainable development goal (SDG) 6, which focuses on ensuring sustainable water
management and sanitation for all, and SDG 12, which is dedicated to sustainable consumption and
production, including improved waste reduction and recycling. However, it should be noted that both
liquid and solid fractions of WWTPs may contain pollutants such as MPs, which are not removed
from WWTPs by current water purification mechanisms.
It should be noted that the Directive on urban wastewater treatment currently in force is more than
30 years old and although the quality of European rivers, lakes, and seas has improved considerably,
certain types of pollution are not covered by the current regulations, a situation that must be corrected
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3Fate and behavior of microplastics inwastewater, accumulation in organisms and effects
to achieve a pollution-free environment by 2050. At present, micropollutants, such as residues of
pharmaceutical and cosmetic products and MPs, are also not included (Directive 91/271/EEC). In
addition, Regulation (EU) 2020/741 of the European Parliament and of the Council of 25 May 2020
concerning minimum requirements for water reuse of recent implementation also does not take into
account MPs.
In this chapter, the focus will be on the problem of MPs in WWTPs, the general characteristics of
these pollutants in wastewater and their distribution and fate along the different treatments commonly
found in conventional WWTPs around the world. It present a review of the behavior of MPs in the
different WW TP units, as well as their accumulation in the sludge. Subsequently, a discussion on how
the MPs from the WWTP can reach the receiving media, such as aquatic or terrestrial media (water
line and sludge line), to finally discuss how the fauna is affected by the entry of the MPs into the
environment.
1.2 MICROPLASTICS IN WASTEWATER TREATMENT PLANTS
The presence of MPs in wastewater was denoted relatively a few years ago (Browne e t al., 2011;
Zhang et al ., 2015), however, numerous recent studies have attempted to address the problematic
of these contaminants to explain their presence, distribution, fate, removal, and characteristics in
conventional wastewater and WWTPs (Bayo etal., 2020; Lares etal., 2018; Lee etal., 2023; Monira
etal., 2023; Sol etal., 2020; Talvitie etal., 2017; Ziajahromi etal., 2017).
1.2.1 Arrival of MPs at WWTPs: sources
The MPs (1 µm–5 mm) that can be found in wastewater come from a multitude of anthropogenic
activities, both domestic and industrial. MPs can be further classified into primary and secondary
MPs. Primary MPs are those that are industrially produced with such size for various applications:
cosmetics (exfoliants, toothpastes, facial cleansing gels, shampoos and shower gels, make-up
(Nawalage & Bellanthudawa, 2022), cleaning products (Anik etal., 2021), abrasive materials, and so
on. Although some regions of the world such as Europe have promoted regulations banning the use of
MPs in cosmetics and personal care products, in many other places these materials are still used. Sun
(2020) reported that up to more than 2000 MPs/g could be found in personal care products, which end
up irretrievably reaching urban WWTPs.
Secondary MPs are those that come from the fragmentation and deterioration of other larger plastic
materials. In both industrial and domestic environments, plastics are often exposed to aggressive
agents and through tearing, friction, or other mechanical means, small fragments break up from the
original material and can end up in wastewater flows. A clear example of this is textile fibers, one of
the main MPs commonly found in wastewater, which come from domestic and industrial washing of
clothes that are woven with synthetic plastic materials such as polyester (PES) or nylon (PA). Several
studies claim that these synthetic fabrics can release from 800 to 1.3 × 107 microfibers in a single wash
(Sillanpää & Sainio, 2017; Yan g etal., 2019), depending on the washing conditions and fabric type.
Other authors have demonstrated the persistence of these microfibers when they reach natural water
bodies and the negative effects, they can have on aquatic living things (Kim etal., 2021, 2023; Mishra
etal., 2019).
Whatever their origin, a large amount of MPs end up in both industrial and urban wastewater
and reach W WTPs, where they are partially removed from the water stream and accumulated in the
sludge generated.
1.2.2 Presence and removal of MPs in wastewater treatment units
The goal of wastewater treatment is to effectively remove or reduce contaminants in water that
represent a hazard to people and the environment if discharged into surface water and/or groundwater
without appropriate treatment (Jasim & Aziz, 2020).
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4Detection and Treatment of Emerging Contaminants in Wastewater
Whatever their origin, a large amount of MPs end up in both industrial and urban wastewater
and reach W WTPs. Conventional wastewater treatment involves a combination of both physical and
biological processes to remove inorganic solids, organic matter, and nutrients from wastewater. The
general terms used to describe the different degrees of treatment, in increasing order, are preliminary,
primary, secondary, and tertiary or advanced wastewater treatment (Janssen etal., 2002).
The presence of plastics and microplastics in water bodies has become a major environmental
challenge of increasing importance. A key challenge is that the available analytical techniques are
relatively inadequate and prevent a thorough understanding of the fate of microplastics in water
and the difficulty of comparing results between authors (Enfrin et al., 2019). The occurrence of
microplastics in wastewater treatment plants raises concern about the quality of treated water and the
reception of treated water into the environment.
One of the main problems in comparing the effectiveness of W WTPs in removing MPs is that not
only are the processes installed in each of the WWTPs different, but there is no standardized method
for analyzing MPs. Some examples of treatments used for the extraction of MPs are shown in Table
1.1, these treatments range from only a filtration, an enzymatic treatment, and alkaline digestion
(KOH 2 M), an advanced oxidation only (H2O2 30%; Wet peroxide oxidation (WPO)), advanced
oxidation with a density separation (Fenton oxidation, density separation, Wet peroxide oxidation
(WPO), density separation) being this density separation ZnCl2 solution (1.8 g/L), ZnCl2 solution
(1. 5 g/cm3), NaCl 5 M and LMT solution (1.62 g/mL). Even some authors like Dronjak etal. (2023)
used a combination of all the treatments, Fenton oxidation, alkaline digestion (KOH 2 M), enzymatic
digestion (2–3 days) + density separation with ZnCl2 solution (1.8 g/L). These differences in treatment
for MP extraction make it difficult to compare the effectiveness and quality of WWTPs. Therefore, a
common method for MP analysis should be standardized.
Another difficulty encountered in the comparison of MPs in WWTPs lies in the size of MPs under
study, Table 1.1 shows the papers that study MPs up to 10 µm (Liu etal., 2020; Mintening etal ., 2017)
to up to 200 µm (Le etal., 2023).
Table 1.1 shows the MPs removal efficiency of the 14 documents under study. These documents
showed a removal efficiency ranging from 68.8 to 99.9%. The WWTP that showed the worst, and the
best removal of MPs was Southern and Central Vietnam, with a treatment process costing Coarse
screen, grit chamber, AS/sequencing batch reactor with UV/trickling filters, and aerated lagoons
(Le etal., 2023). The extraction of microplastics used by the authors was enzymatic treatment. The
concentration of MPs at the inlet of WWTPs varies from 0.92 MPs/L in Hvidovre, Denmark (Liu etal .,
2020) to 1058 in Barcelona, Spain (Dronjak etal., 2023). In effluent, the variations between different
studies range from 0.01 MPs/L in Oldenburg, Germany (Mintening et al., 2017) to 73.25 MPs/L in
Turkey (Akdemir & Gedik, 2023). According to the polymer types identified, PP is the only polymer
reported in all studies, followed by PE which is reported in all the documents except in Vancouver
and Canada (Gies etal., 2018). The remaining polymers identified in most studies are PS, PVC, PET,
PA, and PES.
1.2.3 Presence and accumulation of MPs in sewage sludge
As discussed previously, the presence of MPs in wastewater has been widely analyzed, reporting
that these pollutants are highly removed during the treatment on the water line, although there are
no specific treatments for the removal of MPs in these facilities, the MPs are eliminated from the
water line, being retained, and accumulated in the sewage sludge line (Gies etal., 2018). The sewage
sludge is the main by-product generated at WWTPs, it can be classified into primary sludge, secondary
sludge, and mixed sludge, depending on the operational step of the WWTP in which they are produced
(Casella etal ., 2023). The sewage sludge contains solids from the mechanical treatment primary setting
tank, extracellular polymeric substances (lipids, nucleic acids, proteins, polysaccharides, bacteria, or
microorganisms) from the biological treatment or secondary tank settling tank and water (Melo etal.,
2022); however, the characteristics of each sludge depend on several variables such as; the source,
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5Fate and behavior of microplastics inwastewater, accumulation in organisms and effects
Table 1.1 WWTP location, treatment process, microplastics extraction, influent and effluent concentration, size, removal efficiency, polymer identified, and
reference.
WWTP
Location
Treatment
Process
Microplastic
Extraction
Influent
Concentration
(MPs/L)
Effluent
Concentration
(MPs/L)
MPs size
(µm)
MPs removal
Efficiency (%)
Polymers
Identified
References
Gumi, South
Korea
Grit removal,
A2O, two-stage
sedimentation,
rapid sand
filtration, U V
treatment
Fenton oxidation,
density separation
with LMT
solution (1.62 g/
mL)
102–26 6 0.05– 0.56 Up to 20 >99 PP, PE, acrlylic,
PES/PET, PS, PA,
SBR, PVC, PU
Kim etal.
(2022)
Beijing,
China
Aerated grit
chamber, primary
sedimentation,
A2O, secondary
sedimentation,
denitrification,
ultra-filtration,
ozonation, UV
Wet peroxide
oxidation
(WPO) + density
separation with
ZnCl2 solution
(1. 5 g/cm3)
12.03 0.59 Up to 50 95.16 PET, PES, PP, PE Ya ng etal.
(2019)
Cádiz, Spain Coarse and
fine screening,
degritting and
degreasing, EA
biological reactor,
secondary
sedimentation,
intermittent sand
filtration
Wet peroxide
oxidation
(WPO) + density
separation with
NaCl 5 M
18 5.4 – 8 97.6 0.3–2.4 Up to 100 99.7 PE, PES, PET, PP Martín-
García
etal. (2022)
Vancouver,
Canada
Vertical screening
bars, primary
clarification,
trickling filters,
solids contact
tank, secondary
clarification,
chlorination
H2O2 30% (7
days)
31.1 0.5 Up to 63 99 PS, PES, PA, PP Gies etal .
(2018)
Glasgow,
Scotland
Coarse and
fine screening,
grit and grease
removal, primary
settling, aeration,
secondary
clarification
Filtration 15.7 0.25 Up to 65 98.4 Acrylic, PET, PA,
PES, PE, PS, PU,
PVC, PP
Murphy
etal. (2016)
(Continued)
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6Detection and Treatment of Emerging Contaminants in Wastewater
Table 1.1 WWTP location, treatment process, microplastics extraction, influent and effluent concentration, size, removal efficiency, polymer identified, and
reference (Continued).
WWTP
Location
Treatment
Process
Microplastic
Extraction
Influent
Concentration
(MPs/L)
Effluent
Concentration
(MPs/L)
MPs size
(µm)
MPs removal
Efficiency (%)
Polymers
Identified
References
Karmiel,
Israel
Bar screens, grit
removal, primary
clarification,
biological
nutrient removal
tank, activated
sludge, secondary
clarification,
filtration,
chlorination
Fenton oxidation+
density separation
with NaCl 5 M
65–130 1.97 Up to 0.45 97 PE, PVC, PP, PC,
PTFE, PO, PS,
PU, PA
Ben-David
etal. (2021)
Mikkeli,
Finland
Screening, grit
separation,
primary
clarification,
activated sludge,
secondary
clarification,
disinfection, MBR
pilot plant
Wet peroxide
oxidation (WPO)
57. 6 0.4–1 Up to 250 98.3–99.4 PES, PA, PE, PP Lares etal.
(2018)
Hvidovre,
Denmark
Biological
nutrient removal,
secondary
clarification,
biofilter
(pilot-scale)
H2O2 50% (2
days), enzyme
treatment (6 days),
fenton oxidation+
density separation
with ZnCl2
solution (1.8 g/
cm3)
0.92 0.1 Up to 10 87.9–95.6 PE, PP, PVC,
PES, PS, acrylic,
PA
Liu etal .
(2020)
Barcelona,
Spain
Sieving, gr it
remover,
degrea ser,
primary
clarification,
biological reactor,
secondary
clarification
Fenton oxidation,
alkaline digestion
(KOH 2 M),
enzymatic
digestion (2–3
days) + density
separation with
ZnCl2 solution
(1.8 g/L)
369–1058 13–26 Up to 20 96–98 PE, PP, PVC,
PE-PP, PA, PAN,
PES
Dronjak
etal. (2023)
(Continued)
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7Fate and behavior of microplastics inwastewater, accumulation in organisms and effects
Viikinmäki,
Finland
Primary
clarification, CAS,
denitrification,
discfilter (pilot-
sca le)/RSF/DAF/
MBR
— — 0.005–0.3 Up to 20 95 (DAF) –
99.9 (MBR)
PES, PE, PP,
PS, PU, PVC,
PA, acrylamide,
polyacrylate,
EVA, P P O
Talvitie
etal. (2017)
Oldenburg,
Germany
Primary
treatment
(skimming
tank), secondary
treatment
(nutrient
removal), tertiary
treatment
(maturation
ponds)
Enzymatic
treatment
—0.01–9 Up to 10 93–98 PP, PE, PA, PVC,
PS, PU, EVA,
ABS, PLA, PEST
Mintening
etal. (2017)
Southern
and central
Vietnam
Coarse screen,
grit chamber, AS/
sequencing batch
reactor with UV/
trickling filters
and aerated
lagoons
Enzymatic
treatment
1.86–125 0.14–0.81 Up to 200 68.8–99.9 PE, PP, PES,
acrylic
Le etal .
(2023)
USA Grit removal,
primary
clarification, AS/
trickling filters,
chlorination/sand
filtration/anMBR
(pilot-scale)
Sieving 133 5.9 Up to 20 93.8–99.4 —Michielssen
etal. (2016)
Tur ke y Primary +
secondary
treatment (not
specified)
H2O2 30% (3– 4
days)
—20.5–73.2 5 Up to 45 — PET, PP, PA, PE,
PS, P VC
Akdemir
and Gedik
(2023)
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8Detection and Treatment of Emerging Contaminants in Wastewater
the volume to treat, the generation of waste by the population equivalent, and the type of wastewater
treated (van Haandel & van der Lubbe, 2019).
Sewage sludge has become a valuable resource for the energy and agriculture sector, as it can be
used for bioenergy production and/or as fertilizer for soil amendment following the circular economy
principles of decreasing the generation of waste and encouraging the reuse of a product previously
considered a waste. According to the Sewage Sludge Directive 86/278/EEC of 12 June 1986, the treated
sludge must go through biological, chemical, heat, or any other process to obtain a final product that
does not present any threat to the environment to be reused in agriculture (Helmecke etal ., 2020). The
sludge treatment processes include thickening, stabilization, dewatering, and thermal drying (Mahon
etal., 2017).
The presence of MPs in sludge has been addressed worldwide, these pollutants have been
encountered in sludge during all the processes taking place in the sewage sludge (Hassan etal ., 2023),
therefore a review of the presence, accumulation, effects, and fate of the MPs along the sewage sludge
line is covered below.
Table 1.2 shows the documents submitted for study on WWTP location, sampling collection, the
type of pretreatment for the analysis of microplastics, the type of sludge, the concentration of MPs,
the shape, size, and types of polymers identified. As with the water line, the lack of a standardized
method for the extraction of MPs as well as different types of W WTP treatments makes it difficult to
compare the different studies. Studies show that the predominant form is fibers, present in all studies
where they have been considered, followed by fragments or particles. Regarding the size, the particles
analyzed range from up to 20 µm (Liu etal., 2020; Menendez-Manjon etal., 2022; Mintening etal.,
2017) to 5 mm (Gies etal., 2018).
Considering the type of sludge, it can be observed that primary sludge in most of the articles
studied presents a higher concentration of MPs (0.23–24.6 MPs/g DW), compared to secondary sludge
(0.05–23 MPs/g DW). The dewatered presents a higher amount of MPs, reaching 240.3 MPs/g DW
(Liu etal., 2020). The polymers present in most of the samples are as in the water line PP and PE, as
well as PA.
1.3 CIRCULAR ECONOMY, REGENERATED WATER, AND SLUDGE AS SOIL AMENDMENT:
ENVIRONMENTAL ISSUES
Nowadays, the main challenge for both industrial and municipal utilities is related to the increase of
environmental protection standards and recommendations, which have been included in the circular
economy package (EC).
The European Union Regulation (EU) 2020/741 concerning minimum requirements for water reuse
states in its Annex II, point A) Main elements of risk management, paragraph 6, that consideration
should be given to water quality requirements and their control that are additional to or more stringent
than those specified in Annex I, Section 2, or both, where necessary and appropriate to ensure
adequate protection of the environment and human and animal health, especially if there is scientific
evidence that the risk is from reclaimed water and not from other sources, in particular paragraph e
takes into account other substances of emerging concern, such as micropollutants and microplastics.
In the case of a CE ‘Wastewater Treatment Plant of the Future’, the recovery of water, energy, and
raw materials from available waste streams is strongly recommended. The implementation of CE
solutions in the analyzed facilities is incorporated into many strategies and policy frameworks, such
as national and international (including European) documents (Smol, 2023). Despite this point, it
does not strictly state that MPs must be removed from water and in what percentage. WWTPs are a
pathway for the entry of MPs into both terrestrial and marine environments, so that terrestrial and
aquatic organisms may be exposed. Water reuse, whether from urban, agricultural, industrial, or even
environmental uses, can be an important source of MP input to the environment that must be taken
into account. Many actions are currently being taken to upgrade and build WWTPs that can respond
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9Fate and behavior of microplastics inwastewater, accumulation in organisms and effects
Table 1.2 WWTP location, sampling collection, microplastics extraction, t ype of sludge, MPs concentration, shape, size, MPs identified, and
reference.
WWTP
Location
Sampling
Collection
Microplastic
Extraction
Type of
Sludge
MP
Concentration
(MPs/g DW)
Shape Size
(µm)
MPs
Identified
References
Cádiz, Spain Glass
jars and
screening
though
metal sieve
WPO
(H2O2 + FeSO4)
digestion, UTS
treatment,
and density
separation
(NaCl)
Primary 6. 58–20.40 Fibers and
fragments
(87%)
Up to
100
Acrylate,
PMMA, PE,
PP
Franco etal.
(2023)
Secondary 0.98–1.89
Digested—
anaerobic
digestion
0. 0 2*– 57.18
Australia Glass Jars PLE extraction,
and Pyr-GC/MS
Digested—
composted
0.4–23.5 mg
MPs/g DW
n.d. n.d. PE, PVC, PE,
PP
Okoffo etal.
(2020)
Chengdu,
China
Stainless-
steel shovel
and stored
aluminum
bag
WPO
(H2O2 + FeSO4)
digestion,
density
separation
(NaCl)
Primary 0.23–0.75
Secondary 0.05–0.06 Particles,
debris, and
fibers
Up to
500
PP, PE, PVC,
and PS
Wei etal.
(2022)
Digested—
composting
0.04–0.11
Falconara
Marittina,
Italy
Steel sieves H2O2 digestion,
density
separation
(NaBr)
Primary 1.67 Fragments
(>70%)
Up to 63 PE, PP Pittura etal.
(2021)
Secondary—
WAS
5.3
Digested–
dewatered
4.74
Vancouver,
Canada
Glass jar Oil extraction
protocol + H2O
digestion
Primary 14.9 Fibers 64–5000 PS, Modified
cellulose
Gies etal.
(2018)
Secondary 4.4
Beijing,
China
Glass jars Density
separation
(ZnCl2)
Digested—
dehydrated
2.93–5.33 Pellets and
microbeads
Up to 50 PBA, PE, PA,
PP, rayon,
and PET
Xu etal.
(2020a)
Newport
United
Kingdom
Glass bottles WPO
(H2O2 + FeSO4)
digestion
and density
separation
(ZnCl2)
Primary 24.6 — Up to
1000
—Lofty etal.
(2022)
(Continued)
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10 Detection and Treatment of Emerging Contaminants in Wastewater
Table 1.2 WWTP location, sampling collection, microplastics extraction, t ype of sludge, MPs concentration, shape, size, MPs identified, and
reference (Continued).
WWTP
Location
Sampling
Collection
Microplastic
Extraction
Type of
Sludge
MP
Concentration
(MPs/g DW)
Shape Size
(µm)
MPs
Identified
References
Speyer,
Germany
Aluminum
tins
H2O digestion
and density
separation (SPT)
Digested
sludge—compost
97. 6 6 Fibers Up to
100
PES, PO Tagg etal.
(2022)
Mikkeli,
Finland
Glass flask WPO
(H2O2 + FeSO4)
digestion
and density
separation
(ZnCl2)
Secondary –
activated sludge
23.0 Fibers Up to 63 PES, PE, PA Lares etal.
(2018)
Digested 170.9
MBR 27.3
Leganés,
Spain
Steel mesh H2O digestion+
density
separation
(NaCl)
Digested
sludge—
anaerobic
133 Fibers and
fragments
36–4720 PE, PP,
Acrylic
Edo etal.
(2020)
Dewatering—
soil amendment
101
Wuhan,
China
Glass beaker Density
separation
Dewatered 240.3 Fibers and
fragments
Up to 20 PA Liu etal.
(2020)
Murcia,
Spain
Glass
jars and
screening
though
metal sieve
WPO (H2O2 +
FeSO4) digestion
and density
separation
(ZnCl2)
Dewatered 12–39 Fragments
and fibres
Up to 20 PET, PS, PA,
PVC
Menendez-
Manjon etal.
(2022)
Olderburg,
Germany
Stainless
steel shovel
and stored
in PVC
container
Alkaline
treatment
Primary 1–24 Fragments*
(fibers not
analysed)
Up to 20 PE, PP, PA,
PS
Mintening
etal. (2017)
Devon,
United
Kingdom
Stainless-
steel bucket WPO (H2O2 +
FeSO4) digestion
and density
separation
(ZnCl2)
Mixed sludge—
primary and
secondary
107.5 Fibers and
particle
Up to 50 PES, PVA,
PE.
Harley-Nyang
etal. (2022)
Digested—
anaerobic
digestion
97. 2
Digested – lime
stabilization
37.7
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11Fate and behavior of microplastics inwastewater, accumulation in organisms and effects
to current and future challenges related to environmental protection and should consider the removal
of MPs from both the water line and the sludge line.
Microplastic pollution emerged from the oceans, but it is estimated that soil receives 4–25 times
more plastic debris annually compared to the marine environment. Lofty etal. (2022) indicated that
European agricultural soils are contaminated with among 31 000 and 42 000 tons (considering MPs
1000–5000 µm in size) or 8.6 × 1013–7.1 × 1014 MPs particles (considering MPs 25–5000 µm in size).
The origin of these pollutants is fertilizers reused from wastewater, a practice aimed precisely at
saving raw materials and favoring the circular economy.
The application of sewage sludge on agricultural land has been an acceptable practice until the
increasing presence of MPs appeared as a new environmental threat to terrestrial ecosystems through
the deposition of MPs on agricultural soils. In Canada, concentrations of up to 541 particles MPs/kg
of soil were found in agricultural soils where sewage sludge had been applied, compared to 4 particles
MPs/kg in control soils where no sewage sludge had been applied, meaning that land application of
sewage sludge is contaminating agricultural soil with MPs (Crossman etal., 2020).
According to these results, it is estimated that wastewater treatment plants in countries such as
Denmark, Sweden, or Norway apply between 63 000 and 430 000 tons MPs/year to agricultural soils
(Nizzetto etal., 2016).
Based on average application rates of sewage sludge on agricultural soils, it is estimated that the
mass of MPs reaches values between 31 000 and 42 000 tons/year for microplastics size between
1000 and 5000 µm. To face this problem, it is necessary to understand the transport of MPs in the
environment, the processes of removing MP in sewage treatment plants, the concentration of MPs
in the sewage sludge and to provide more information on the MP balance and the contamination of
agricultural soils. The removal of MPs from the sludge line of a WWTP is paramount to the use of soil
amendment or fertilizers from sewage sludge, as we would be adding a MPs contamination problem
to the terrestrial environment.
1.4 ACCUMULATION OF MICROPLASTICS IN ORGANISMS AND EFFECTS
WWTPs are a pathway for the entry of MPs into both terrestrial and marine environments, so
terrestrial and aquatic organisms may be exposed. Ingestion is the main interaction between
organisms and microplastics, possibly due to confusion with food, although adsorption processes may
also occur (Dovidat etal., 2020; Ribeiro etal., 2019). The potential of microplastics to cause harm to
marine organisms has been widely documented and leads to the following adverse effects: reduced
feeding rate, reduced predatory performance, physical damage, induction of oxidative stress, effects
on reproduction, decreased neurofunctional activity, oxidative damage, development of pathologies,
mortality, among others (de Sá etal., 2018).
In conjunction with this, the large specific surface area of microplastics facilitates their adsorption
of organic contaminants, as demonstrated for polybrominated diphenyl ethers (PBDEs), polycyclic
aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), endocrine disruptors, and heavy
metals. This ability of microplastics to serve as vectors may result in bioaccumulation of these and
potentially other contaminants (Xu etal., 2020b).
Table 1.3 shows the accumulation of microplastics in organisms and effects: Specie analyzed, type of
polymer, characteristics of the MPs, effects, scale study, and reference. The difficulty of analyzing MPs
in the field, in uncontaminated individuals and with specific concentrations or types of polymers, means
that to better understand the toxic effects, this must be done in a controlled laboratory environment. PE,
PS, PET, and PVC are the most common polymers used for the studies because of their composition or
abundance. Some of the effects caused by MPs are delayed germination due to their accumulation in the
seed case in vegetables, growth, and reproductive stunting or even inhibition (Schöpfer etal., 2020; Zhang
etal., 2023a; Zhong etal., 2021), increased bioaccumulation of ATZ in species, especially in aged species
(Song etal ., 2023), and transport of MPs through the vascular pool to the vapor and leaves (Li etal ., 2020).
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12 Detection and Treatment of Emerging Contaminants in Wastewater
Table 1.3 Accumulation of microplastics in organisms and effects. Specie analyzed, type of polymer, characteristics of the MPs, effects, scale
study and reference.
Specie
Analyzed
Polymer Characteristics of
the MPs
Effects Scale
Study
References
Eisenia Fetida PE Shape: Spheres: Fragments
Size: -
MPs concentration: 0.2 g
– Increase the bioaccumulation of ATZ in
both species, especially in aged-PE
Lab Song etal.
(2023)
Metaphire
Guillelmi
PE-aged
Bufo gargarizans
(Tadpoles)
PS Shape: spheres
Size: 1 and 10 µm
MPs concentration: 2.5% (w/v)
– Growth and development of tadpoles delayed
– 10 µm MPs bioaccumulated in the digestive
tract: altered gut biota changing the
homeostasis.
– 1 µm MPs affected host tissues: altered the
cellular response and neural functions,
upregulated protein synthesis and
mitochondrial energy
Lab Zhang etal.
(2023b)
Eisenia Fetida PE Shape: -
Size: 100–200 µm
MPs concentration: 2000,
50 000 and 200 000 particles/
kg sludge
– MPs size decrease in earthworm casts
– Oxidative stress and neurotoxicity damage
at high concentrations of MPs
Lab Zhong etal.
(2021)
Folsomia
candida
PVC Shape: -
Size: 80–250 µm
MPs concentration: 1 g/kg soil
– Reduction in growth and reproduction
– Increased bacterial diversity and altered gut
microbiota
– Enhanced isotopic composition (δ15N and
δ13C) values of collembolan tissues
Lab Zhu etal .
(2018)
Achatina fulica PET Shape: Fibers
Size: 76.3–1257 µm
MPs concentration: 0.014, 0.14,
0.71 g/kg soil
– Reduced food intake and excretion
– Villi damage in the gastrointestinal walls
– Oxidative stress in the individuals of the
0.71 g/kg soil
Lab Song etal.
(2019)
Eisenia Fetida PE Shape: -
Size: 70–250 µm
MPs concentration: 0.5%, 1%,
2%, 5%, 7%, 14% (w/w)
– SOD, CAT, POD, GST, and AchE activities
showed an inhibition-stimulation pattern.
– Indicating neurotoxicity and oxidative stress
– Gut microbiota variation decreased
– No difference between PLA and PE on day 28
Lab Yu etal .
(2022)
PLA
Caenorhabditis
elegans
LDPE Shape: fragments
Size: LDPE 57 ± 40 µm
PLA/PBAT 40 ± 31 µm
MPs concentration: 1, 10,
100 mg/L
– Reproduction inhibition Lab Schöpfer
etal. (2020)
PLA
PBAT
(Continued)
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13Fate and behavior of microplastics inwastewater, accumulation in organisms and effects
Triticum
aestivum L.
Lactuca sativa L.
PS
PMMA
Shape: spheres
Size: PS 0.21 ±
0.05 µm–1.93 µm ± 0.09 µm
PMMA:
0.18 ± 0.05 µm–2 ± 0.1 µm
MPs concentration: 0.5, 5 and
50 mg/L
– Transportation of MPs through vascular
assembly to steam and leaves
Lab Li etal .
(2020)
Daucus carota PES, PA,
PP, LDPE,
PET, PU,
PS, PC
Shape: Fibers, films, foams,
fragments
Size: Fibers up to 5 mm
Films, foams and fragments up
to 5 mm2
– Shoot and root mass increased in presence
of MPs
– MPs negatively influenced soil aggregation
and microbial activity
Lab Lozano etal.
(2021)
Spirodela
polyrhiza
PS Shape: Spheres
Size: 50–500 nm
MPs concentration: 102 to 106
particles/mL
– External adsorption of MPs to the roots
– No significant effects on growth or
chlorophyll concentrations
Lab Dovidat etal.
(2020)
Glycine max L .
Merrill
PS Shape: -
Size: 100 nm–100 µm
MPs concentration: 10 mg/kg
– MPs damaged the root and inhibited its
activity, decreasing the abundance of
microbial in rhizosphere
– Genotoxicity in presence of MPs was detected
– MPs enhanced the toxic effects of polycyclic
aromatic hydrocarbons such as phenanthrene
Lab Xu etal.
(2021)
Oryza sativa PS Shape: -
Size: 20 nm
MPs concentration:
10–100 mg/L
– MPs decreased root length and weight
– PS induced oxidative stress and damage in
rice roots
Lab Zhou etal.
(2021)
Cucumis sativus
L.
PE, PA,
PLA
Shape: -
Size: 13–500 µm
MPs concentration:
40–1000 mg/L
– PE MPs cases higher Cr (VI) accumulation
and phytotoxicity than PA and PLA
– MPs type affect negatively plant growth and
chlorophyll content
Lab Zhang etal.
(2023a,
2023b)
Lepidum sativum —Shape: -
Size: 50–4800 nm
MPs concentration: 103–10
particles/mL
– MPs cause late germination due to
accumulation on seed case
– MPs cause significant impact on root growth
Lab Bosker etal.
(2019)
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14 Detection and Treatment of Emerging Contaminants in Wastewater
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© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0019
Mahak Jain1, Abhradeep Majumder2, Pubali Mandal3, Shalini Singh4, Partha Sarathi Ghosal1
and Manoj Kumar Yadav4*
1School of Water Resources, Indian Institute of Technology Kharagpur, Kharagpur 721302, India
2School of Environmental Science and Engineering, Indian Institute of Technolog y Kharagpur, Kharagpur 721302, India
3Department of Civil Engineering, Birla Institute of Technolog y Pilani, Pilani 333031, India
4Department of Civil and Environmental Engineering, Indian Institute of Technology Patna, Patna 801106, India
*Corresponding author: mkyadav@iitp.ac.in
ABSTRACT
Pharmaceutically active compounds (PhAC) are pervasive in aqueous environments, and their presence poses an
ever-increasing threat to aquatic creatures and all associated living forms. Most PhACs are extremely hydrophilic
and have a complicated molecular structure, preventing them from being destroyed by traditional wastewater
treatment methods. In addition, these contaminants are present at such a low concentration that their detection
poses a significant challenge. Researchers have utilized advanced oxidation processes to degrade these chemicals
over time. However, most studies have been conducted on the lab scale and do not function well for real wastewater
since many interfering substances are present. In addition, these techniques are expensive and result in the
production of harmful byproducts. To combat the PhACs, it is vital to develop a sustainable economic strategy.
This book chapter discusses the occurrence of PhACs in wastewater, their potential environmental impacts, and
the necessary procedures for accurately quantifying these compounds. The book addresses the possibilities of
biological systems, such as constructed wetlands (CW) and bioelectrochemical systems (BES), in the hunt for a
sustainable method of eliminating PhACs. CWs have been selected because they are robust systems with several
simultaneous removal mechanisms. BES have also demonstrated considerable potential for treating these
substances in wastewater and producing bioelectricity. In addition, the chapter discusses an emerging technology,
that is, hybrid CW–BES systems, which utilize the benefits of both CW and BES and may prove to be an efficient
approach to treating wastewater, removing PhACs, and generating electricity simultaneously.
2.1 INTRODUCTION
The onset of the 21st century is marked by the rapid detection of pharmaceutically active compounds
(PhACs) in various aqueous environments. The improvement in healthcare facilities and medicines has
Chapter 2
Occurrence and detection of
pharmaceuticals in wastewater and
its subsequent treatment using
constructed wetlands,
bioelectrochemical systems and
their combination
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20 Detection and Treatment of Emerging Contaminants in Wastewater
led to increased consumption of pharmaceuticals. Most unmetabolized fractions of pharmaceuticals
are excreted as feces or urine by human bodies. As a result, PhACs and metabolites of pharmaceuticals
are frequently detected in hospital and municipal wastewater. The increase in medicine consumption
has resulted in the shift in research toward pharmaceutical removal and treatment of hospital
wastewater in the last 10 years or so (Majumder etal., 2021; Parida etal., 2022). The country/region-
wise studies over the last 20 years pertaining to the occurrence of PhACs in aqueous environments
are depicted in Figure 2.1. Articles that come under the topic containing the words, ‘occurrence of
pharmaceuticals’ AND ‘water’, were considered for the study. The search was restricted to document
type ‘articles’ only. It was observed from Figure 2.1 that research on PhACs occurrence in the early
part of the 21st century (2001–2005) was only restricted to developed countries, such as the USA,
Germany, Spain, Italy, and France. After 2006, Asian countries, such as South Korea, Japan, and
China, started contributing to this field, which may be due to the requirement of high-end analytical
instruments, such as high-performance liquid chromatography (HPLC), gas chromatography (GC),
liquid chromatography coupled with mass spectrometry (LC–MS), gas chromatography coupled with
mass spectrometry (GC–MS), and others. Furthermore, the presence of other non-target organic
compounds and interfering agents often make the detection and quantification of the PhACs, a
challenging task (Boulard etal., 2020; Stamatis & Konstantinou, 2013). However, with the passage of
time and the advent of new technologies, research in this field got a significant boost. The number of
research articles published between 2011 and 2020 was found to be almost five times higher than that
between 2001 and 2010. Furthermore, the articles were reported from countries all over the globe,
indicating the presence of PhACs in aqueous matrices is a global problem.
Although the PhACs are found in almost all aqueous environments, their concentration is very low,
that is, in the range of µg/L to ng/L. However, the PhACs have the potential to cause significant harm
to the environment even at low concentrations (Majumder etal., 2019). As a result, it is important to
detect the presence of these contaminants. In water and wastewater, there are innumerable PhACs
and their metabolites detected in water. Each of these compounds has a different effect on non-target
Figure 2.1 Country-wise trend in literature published on analysis of PhACs (source: Scopus database).
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21Occurrence and detection of pharmaceuticals in wastewater
species. As a result, collectively, all these compounds can significantly disrupt ecosystems. Hence, it
has become mandatory to address the removal of these compounds (Majumder etal., 2019). PhACs
are highly mobile in the aqueous phase and have complex molecular structures. Furthermore, many
of the PhACs are hydrophilic in nature (Majumder et al., 2019). Hence, it is difficult to remove
the PhACs by conventional treatment methods. When conventional treatment methods are coupled
with advanced treatment processes, the overall cost of the process increases. Hence, to achieve
a sustainable treatment of PhACs from wastewater, it is necessary to simultaneously remove the
contaminants and recover resources in some form. Constructed wetlands (CWs) have proved to
be effective in removing a wide range of contaminants due to the multiple removal mechanisms
taking place simultaneously. However, CWs need an extensive amount of aeration for their proper
functioning. On the other hand, microbial fuel cells (MFC) have been known to convert wastewater
to electrical energy. In this context, constructed wetland-microbial fuel cell (CW–MFC) systems
have been developed that combine the benefits of CW and MFC (Fang etal., 2015; Liu etal., 2022;
Lutterbeck etal., 2022). While the CWs are responsible for bringing down the organic loading and
degrading the PhACs, the energy recovery in the form of electricity may lower the costs of operation
and maintenance of the treatment unit. CW–MFC has been used to treat sewage from homes, treat
wastewater from factories, and control pollution from non-point sources in cities (Fang etal., 2015;
Liu etal., 2022; Lutterbeck etal., 2022).
In this chapter, the different types of PhACs detected in aqueous environments have been discussed,
along with the concentration of few of the most commonly detected PhACs. The environmental impact
Figure 2.2 Challenges in the analysis of PhACs.
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22 Detection and Treatment of Emerging Contaminants in Wastewater
of the PhACs and the challenges in detecting these PhACs will also be discussed. The difficulties in
removing the PhACs using conventional treatment processes and the applicability of CW and BES in
removing PhACs from wastewater have been addressed. Lastly, the performance of CW–BES-based
systems to simultaneously treat wastewater, remove PhACs and generate electricity.
2.2 TYPES OF PHACS DETECTED IN WASTEWATER AND THEIR PHYSICOCHEMICAL
PROPERTIES
Researchers have documented the presence of a large range of different PhACs in variable
concentrations in different aqueous environments (Majumder et al., 2019). These compounds are
difficult to remove due to their high mobility and hydrophilicity, and they remain in the aqueous
environment for a prolonged duration (Majumder etal., 2019). Therefore, research into the treatment
of PhACs has been given a higher priority.
The most common types of PhACs detected in aqueous environments are analgesics, antibiotics,
β-blockers , and endocrine -disr upting compou nds (EDC). Apa rt from the se, antiepilep tics and sti mulants,
such as carbamazepine and caffeine, are also frequently detected in various aqueous environments
(Majumder et al., 2019). In Table 2.1, the different classes of pharmaceuticals, their physicochemical
properties, and their concentration in surface water, municipal wastewater, and hospital wastewater
have been depicted. In this chapter, the most commonly occurring PhACs in different aqueous
environments have been considered (Majumder et a l ., 2019; Parida e tal., 2022; Pubchem, 2023; Saidulu
eta l ., 2021). The PhACs which are associated with a low octanol–water partition coefficient (log kow) do
not get absorbed easily. Furthermore, the dissociation constants (pKa) of the PhACs indicate the charge
of these compounds in water (Majumder et al., 2019; Tran etal., 2018). If the particles are charged,
then it is difficult to remove by conventional sedimentation or adsorption processes. Furthermore, the
toxicity and complex structure of these compounds prevent biodegradation. Although these PhACs
are removed by AOPs, they significantly increase the cost of treatment. Furthermore, the AOPs have
only proved to be effective when the water or wastewater matrix is free from suspended organic or
inorganic matter and interfering agents. Hence, AOPs are not standalone processes, and they need
to be implemented after undergoing pre-treatment of the wastewater (Majumder et al., 2022; Santos
etal., 2009; Tran etal., 2018). Hence, researchers have shifted their focus to developing cost-effective,
sustainable treatment technologies that can remove the PhACs.
2.3 ENVIRONMENTAL IMPACT OF THE PRESENCE OF PHACS IN WASTEWATER
The concentration of the PhACs is quite low in different water matrices (Table 2.1). However,
prolonged exposure to these contaminants over a period of time can significantly affect the non-
target species. Analgesics, such as diclofenac, ibuprofen, naproxen, paracetamol, and others, may
cause cytological changes in different vital organs of fishes. The non-target species, upon exposure,
may also develop gastric ulceration, dyspepsia, bowel inflammation, and mucosal damage, and
their cardiovascular and central nervous system may also be affected (Majumder et al., 2019).
Antibiotics in the aqueous environment may lead to the formation of resistant genes and bacteria.
The extended-spectrum beta-lactamase (ESBL) producing bacteria develop a resistance to the
exposed antibiotics and multiply, thus leading to the formation of antibiotic-resistant bacteria.
These resistant bacteria are capable of causing much more virulent diseases (Majumder e ta l . , 2021).
Furthermore, the immune system of non-target species may also be get affected (Majumder etal.,
2019). β-blockers may hinder the growth of embryonic stem cells and cause cardiovascular and
neural problems among non-target species. Antiepileptics and stimulants may hamper the growth
of embryonic cells, cause panic disorders, and increase plasma epinephrine levels among non-target
species. EDCs can lower sperm count among male fishes and lead to abnormal sexual development
(Majumder etal., 2019).
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23Occurrence and detection of pharmaceuticals in wastewater
Table 2.1 Physicochemical properties of PhACs and their concentrations in different aqueous environments.
PhACs Class Molecular
Weight
pKaLog kow Surface
Water (µg/L)
Municipal
Wastewater (µg/L)
Hospital
Wastewater (µg/L)
Codeine Analgesics of
non-steroidal
inflammatory drug
(NSA ID)
299 10.6 1.19 0.31 ± 0.41 8.11 ± 13.70
Diclofenac 296 4.15 4.52 1.22 ± 2.64 3.52 ± 6.59 1.50 ± 1.50
Ibuprofen 207 4.9 3.97 9.65 ± 24.12 21.19 ± 18.41 16.61 ± 15.11
Naproxen 229 4.15 3.18 1.67 ± 2.98 4.12 ± 3.70 13.82 ± 20.41
Acetaminophen 152 9.4 0.46 18.04 ± 39.45 222.71 ± 235.35 109.40 ± 131.86
Salicylic acid 137 3.49 1.19 5.35 ± 7.81 6 4.41 ± 97.7 9
Ciprofloxacin Antibiotics 332 6.25 0.28 1302.78 ± 2905.34 7.30 ± 9.89 53.21 ± 112.72
Sulfamethoxazole 254 1.6, 5.7 0.89 4.45 ± 11.65 13.42 ± 27. 59 6.09 ± 7.86
Trimethoprim 291 7.1 2 0.91 1.78 ± 2.78 9.96 ± 23.68 6.23 ± 11.61
Ery thromycin 734 8.8, 8.9 3.06 1.15 ± 2.38 3.75 ± 4.38 0.67 ± 0.51
Azithromycin 749 8.74 4.02 0.02 300.00±7.25 ± 11.50
Norfloxacin 320 6.34, 8.75 0.46 260.07 ± 367.6 0 1.10 ± 1.40 4.57 ± 4.74
Levofloxacin 362 6. 24, 8.74 −0.39 0.04 38.57 ± 74.2 9 8.80
Ofloxacin 362 5.9 7, 9. 2 8 −0.39 2 7. 52 ± 38.86 2.38 ± 3.20 6.99 ± 7.97
Atenolol β-blockers 267 9.6 0.16 6.56 ± 11.0 4 38.99 ± 98.43 4.65 ± 5.10
Metoprolol 268 9.6 1.88 3.11 ± 4.02 190.29 ± 424.69 3.24 ± 2.49
Carbamazepine Antiepileptics 237 13.9 2.45 0.54 ± 0.96 2.52 ± 5.39 2.00 ± 2.37
Caffeine Stimulants 194 10.4 −0.07 35.57 ± 62.38 61.68 ± 60.72 124.50 ± 133.77
Estriol EDCs 287 10.54 2.45 0.13 ± 0.22 0.28 ± 0.46 0.25 ± 0.18
17β estradiol 271 10.46 4.01 0.04 ± 0.04 0.07 ± 0.11 0.43 ± 0.44
Source: Majumder etal. (2019), Parida etal. (2022), Pubchem (2023) and Saidulu etal. (2021).
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24 Detection and Treatment of Emerging Contaminants in Wastewater
2.4 CHALLENGES IN DETECTING PHACS IN WASTEWATER AND STRATEGIES FOR THEIR
EFFECTIVE ANALYSIS
One of the biggest challenges in the detection of PhACs is their low concentrations in the aqueous
environment. Most of the instruments, that is, HPLC and GC have a limit of quantification of around
1 µg/L, whereas many of the PhACs in surface water or groundwater are present in the range of ng/L
to pg/L (Bexfield etal., 2019). Furthermore, since these are organic compounds, they may undergo
transformations from the time of sampling to the time of analysis. The PhACs may undergo bacterial
degradation or photolysis, thereby lowering their initial concentration. Furthermore, PhACs may get
adsorbed onto the walls of the container or suspended solids present in the container, thereby leading
to erroneous analysis. Additionally, since real wastewater samples contain many other organic
substances and interfering agents apart from the target PhACs, their quantification may be affected
(Mompelat et al ., 2013). The different issues and challenges in the detection of PhACs have been
illustrated in Figure 2.1.
There are certain protocols that, if followed, may lead to accurate analysis and thereby help in
overcoming the challenges pertaining to the detection and quantification of PhACs. Firstly, thorough
blanking should be carried out. Blanking of samples should include field blank, instrument blank,
equipment blank, method blank, and trip blank (USEPA, 2000). The sample containers should be
properly washed and made sure that there is no prior contamination. To prevent microbial degradation,
the samples can be preserved by adding sodium azide, formaldehyde, or methanol, which are toxic
to microorganisms (Guzel etal., 2019; Havens etal., 2010; Mompelat etal., 2013; Vanderford etal.,
2003, 2011). Lowering the pH of the sample by adding hydrochloric acid and nitric acid also prevents
bacterial growth (Guzel et al., 2019; Havens et al., 2010; Mompelat et al., 2013; Vanderford et al.,
2003, 2011). To prevent the degradation of the PhACs by photolysis, the samples should be stored in
amber bottles. Amber bottles prevent the entry of light inside the storage containers. Also, storing the
samples at less than 4°C prevents microbial activity (Mompelat etal., 2013). These are few of the steps
that should be carried out to maintain the concentration of the PhACs from the time of sampling to
the time of analysis.
As mentioned earlier, a major problem associated with the quantification of PhACs is the
concentration of the compounds in the aqueous environment (Bexfield etal., 2019; Majumder etal.,
2019). Hence, it is required to increase the concentration of these compounds in the solution for
their detection. However, increasing evaporation may lead to the breakdown of the organics. Even
concentrating the solutions by nitrogen purging may be a time-consuming process. In this context,
extraction is carried out using different methods, such as solid-phase extraction (SPE), solid-phase
micro-extraction (SPME), liquid-phase extraction (LPE), accelerated solvent extraction (ASE),
microwave-assisted extraction (MAE), ultrasonic-assisted extraction (UAE), Soxhlet extraction
(SE), membrane extraction, lyophilization, and others (Fatta-Kassinos et al., 2019; Kostopoulou &
Nikolaou, 2008; Pavlović etal., 2007). Among these processes, the SPE is the most commonly used
process.
In the SPE, along with the concentration of the target analytes, the interfering agents can also be
filtered out. The SPE technique is based on the basic principle of transferring target analytes from a
liquid phase to a solid phase (cartridges containing a sorbent), which can retain the target analytes
and can subsequently be stripped by an appropriate solvent. This transfer of target analytes from a
liquid phase to a solid phase is accomplished by the SPE technique. A typical liquid sample that needs
to be examined contains a number of components that cause interference in addition to the analyte
that is of interest. The SPE process typically consists of four phases, which are carried out in the
sequence listed in order to successfully isolate the target analyte from the interfering components
(Andrade-Eiroa etal., 2016; Meng etal., 2021).
In the initial stage, cartridge columns are put through a first pass with either an organic solvent or
water. This process is referred to as conditioning, and its primary purpose is to enhance the effective
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25Occurrence and detection of pharmaceuticals in wastewater
surface area of the sorbent material contained within the cartridge while simultaneously removing
any interferences. After allowing the sorbent to dry out, the next step involves loading the cartridges
with a water sample that contains PhAC. The interference analytes are allowed to pass through with
the sample solution, while the target analytes are taken up by the sorbent and stored there. The
subsequent stage is washing, which involves removing interferences and components from the sorbent
that are not the target analytes. This phase comes after the process in which the target analytes are
determined. The final stage is known as elution, and it is the process in which organic solvents are
circulated through the cartridges. During this step, desorption takes place, which moves the target
analytes from the solid phase (sorbent) to the liquid phase (organic solvent) (Andrade-Eiroa etal.,
2016; Meng etal., 2021).
The whole concentration of the analytes that are present in the liquid sample is absorbed into
the cartridges through the use of SPE, which is one of the primary reasons why this technique is so
important to the quantification of the analytes. If the concentration of the analytes in the sample is
low, a large volume of the sample can be run through the cartridges to maintain a sufficient quantity
of the analyte in the SPE cartridges. This is possible since the concentration of the analyte in the
sample is low. When these target analytes are eluted in a relatively lesser amount of organic solvent,
the concentration of the analytes in the solvent gets enhanced by the sample-to-solvent volume ratio,
which subsequently facilitates better detection and quantification. Before analyzing the sample, it
is possible to further concentrate it by subjecting the elute containing the target analytes to a mild
stream of nitrogen gas (Afsa etal., 2020; Andrade-Eiroa et al., 2016; Biel-Maeso etal., 2018; Meng
etal., 2021). Only after this can real water samples containing PhACs be accurately quantified using
HPLC or GC.
2.5 CHALLENGES IN REMOVING PHACS FROM WASTEWATER
Most of the PhACs are characterized by high molecular weight, complex molecular structure, high
hydrophilicity, and pose toxicity to microorganisms. The complex molecular structure prevents these
molecules from being easily degraded. Conventional wastewater treatment plants relying on activated
sludge processes have not proved to be effective in removing the PhACs. This is mainly because the
primary removal mechanism of the PhACs in these systems is biodegradation, and many of the PhACs
are resistant to biodegradation due to their toxic nature. Another removal mechanism involved in the
removal of PhACs is the adsorption in the suspended matter. However, many PhACs have low log kow
values, which makes them hydrophilic. Hence, they do not get easily removed by adsorption. In the
case of water treatment plants, the primary sedimentation tanks, clariflocculator, and sand filtration
are not designed to remove the PhACs. Furthermore, it has been observed that when chlorination
is carried out, the residual chlorine reacts with metabolites of the PhACs present in the effluent to
produce toxic disinfection byproducts (Qadafi etal., 2023).
Among membrane-based treatment processes, a high degree of PhAC removal has been observed
only when nanofiltration or reverse osmosis is used. However, the drawback of these processes is
that they require a high operating cost and the membranes are subjected to fouling (Perreault etal.,
2016; Prado etal., 2017). Other advanced treatment processes, such as adsorption, have proved to be
effective. However, adsorption produces a significant amount of sludge, which needs to be disposed
of. Also, adsorption can be used only as a tertiary treatment process and cannot be used to treat
raw wastewater (Bizi, 2020). Similarly, in AOPs, such as photocatalysis, Fenton process, electro-
oxidation, and others, which rely on the generation of oxidizing radicals for the degradation of PhACs,
a pre-treatment of the wastewater is necessary (Majumder etal., 2022). Often due to the presence of
suspended solids, organic matter, and other interfering agents, the oxidizing radicals get scavenged
(Majumder et al., 2022). This significantly affects the removal efficiency of the AOPs. Hence, AOPs
should also follow a pre-treatment process where the majority of suspended matter and organics are
removed.
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26 Detection and Treatment of Emerging Contaminants in Wastewater
Another downside to the degradation of PhACs is the formation of degradation byproducts or
transformation products (TPs). Often during biological degradation or oxidative degradation of the
PhACs, complete degradation is not attained. As a result, TPs are formed, which may at times, have
toxicity more than the parent compound (Gogoi etal., 2018; Li etal., 2023; Villarín & Merel, 2020).
The toxicity of the formed TPs may further affect the aquatic ecosystem. Hence, the treatment provided
should be such that relatively low toxic products are formed, and even if they are formed, they are at
concentrations low enough to not significantly harm the environment.
The removal of PhACs by conventional treatment processes has not proved to be effective while
incorporating advanced oxidation processes (AOP)s with the conventional treatment processes
increases the overall cost of the system. In this context, it has become necessary to come up with a
low-cost sustainable treatment system that can address all the concerns stated above. In this context,
the role of constructed wetlands, bioelectrochemical systems, and their combination in terms of the
removal of PhACs have been discussed in the following sections.
2.6 PERFORMANCE OF CW IN REMOVING PHACS
The CWs have shown a high degree of PhAC removal as compared to other conventional biological
processes because of the numerous removal mechanisms involved in their degradation (Jain et al.,
2023). However, the primary mechanisms involved in the removal of PhACs in CWs are the microbial
degradation, plant uptake, and adsorption by the media (Jain et al., 2023). CWs have been even
more efficient in treating real wastewater on numerous occasions because it help removing soluble
and insoluble organic matter. The substrate present in the CWs helps remove a major portion of the
suspended and dissolved organic and inorganic matter, which allows the microbial degradation of
the PhACs to take place. However, hydraulic retention time (HRT) is an important factor in CWs.
Sufficient time should be provided to allow microbial degradation or plant uptake of the PhACs to
take place (Kamilya etal., 2023; Yates etal., 2016).
The removal of PhACs using CW-based systems has been shown in Figure 2.3a. It has been
observed that the removal efficiency of PhACs has varied quite a lot in the systems. Analgesics, such
as naproxen and salicylic acid, exhibited excellent removal. On the other hand, carbamazepine and
a few antibiotics showed very low removal. This may be because of the low biodegradability of these
compounds (Saidulu et al ., 2021). Furthermore, many of the PhACs, such as antibiotics, are toxic
to bacteria, thereby preventing microbial degradation. The other driving factor responsible for the
removal of PhACs in the CWs is aeration. Often aeration facilitates the biodegradation process of the
PhACs (Auvinen etal., 2017; Sochacki etal., 2018).
Apart from the removal of organic matter, suspended matter, and recalcitrant organics, PhACs can
also be used to recover nutrients, such as ammonia and phosphorous. Heavy metal recovery is another
advantage of CWs. These systems can significantly contribute to the circular economy by recovering
valuable resources from wastewater (Guo etal., 2020; Kamilya etal., 2022). Therefore, the CWs have
been a robust system that can tackle high-strength wastewater, remove PhACs, contribute to the
circular economy, and also improve the aesthetics of the place. Furthermore, due to the ability of the
CWs to tackle fluctuations in organic and hydraulic loading, any pre-treatment is not mandatory (Jain
etal., 2023). However, the drawbacks of this process involve high HRT and large land requirements
(Jain etal., 2020, 2023). The schematic of a typical CW and its applicability in various aspects of
sustainable wastewater management options has been depicted in Figure 2.4.
2.7 PERFORMANCE OF BES IN REMOVING PHACS
Bio-electrochemical systems (BES) have the potential to convert the chemical energy present in
wastewater and lignocellulose biomass into various forms of energy, including electricity, hydrogen,
and other chemical compounds. In this process, the organic molecules are degraded by the bacterial
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27Occurrence and detection of pharmaceuticals in wastewater
Figure 2.3 Removal of different PhACs using (a) CW, (b) BES, and (c) CW–BES based systems (source: Ahmad etal.,
2022; Hu etal., 2021; Huang etal., 2021; Kamilya etal., 2023; Li etal., 2 019; Luo etal., 2023; Pun etal., 2019; Thapa
etal., 2022; Wang etal., 2015; Xu etal., 2022; Yan etal., 2019).
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28 Detection and Treatment of Emerging Contaminants in Wastewater
population in the wastewater. Electrons generated through the process of oxidation can be harnessed
to produce energy that can subsequently be utilized for the creation of practical applications. The
prevalent types of bioelectrochemical systems (BES) are categorized based on the biocatalysts utilized
or their mode of application. These include microbial fuel cells, plant microbial fuel cells, microbial
electrolysis cells (MEC), enzymatic fuel cells (EFC), microbial solar cells, and others (Kelly & He,
2014; Pant etal ., 2012; Wang & Ren, 2014). The effectiveness of BES systems in removing PhACs has
been shown in Figure 2.3b. The anode in the BES hosts a large consortium of microorganisms that
help in the production of electricity and also in the degradation of PhACs. In the BES, the PhACs
can get degraded at the cathodic and the anodic chambers via different redox processes (Thapa
etal., 2022; Zhang etal., 2015). As depicted in Figure 2.3b, most of the systems have shown a very
good removal efficiency. However, quite a few of the studies have been carried out using synthetic
wastewater.
Apart from removing PhACs, BES are also efficient in removing organic matter. However, the
removal of insoluble inorganic fractions or suspended solids from the wastewater using a stand-alone
BES is not substantial (Kim etal ., 2016). As a result, for enhanced performance of the BES, employing
a pre-treatment process to reduce the load of suspended solids is important. BES-based systems have
been known to recover electricity and contribute toward the sustainability of the system and circular
economy. Apart from electricity, modifications to BES can also bring about nutrient recovery in the
form of nitrogen and phosphorous (Kelly & He, 2014; Pant etal., 2012; Wang & Ren, 2014).
However, the operation and maintenance of the BES are not as convenient as that of the CWs. In
BES, it is required to maintain anaerobic conditions in the anodic chamber and aerobic conditions in
the cathodic chamber. Failing to maintain this will hamper the performance of the BES. As a result of
this, the BES cannot also handle fluctuations in hydraulic loading. It is a much more sensitive system
as compared to CWs and requires thorough maintenance to bring out the best performance of BES.
The schematic of a typical BES and its applicability in various aspects of sustainable wastewater
management options has been depicted in Figure 2.4.
2.8 PERFORMANCE OF HYBRID CW–BES SYSTEM IN REMOVING PHACS
In CW–BES systems, the dissolved oxygen of the wastewater decreases with the increase in substrate
depth, and anaerobic conditions start to prevail. The cathode is usually kept at the top of the substrate,
where it is exposed to air (air cathode) or water (in the case of floating wetlands) (Lutterbeck etal.,
2022; Mu etal., 2020). CW–BES has the advantages of CWs, such as the ability to handle fluctuations
in organic and hydraulic loading, resource recovery, multiple removal mechanisms for the removal
of PhACs, and others. Also, due to the difference in dissolved oxygen in the cathodic chamber (above
the substrate) and anodic chamber (below the substrate), there is a growth of electrogens at the anode,
which uses wastewater as a source of carbon and releases electrons, thereby initiating the transfer of
electrons from anode to cathode. This leads to the generation of electricity (Lutterbeck etal., 2022;
Mu etal., 2020).
Apart from the generation of electricity, the CW–BES has shown the potential to degrade PhACs
(Figure 2.3c). It was observed that CW–BES showed better removal of antibiotics as compared to
other PhACs. However, studies considering the removal of PhACs from real wastewater are limited,
and hence, it is too early to remark anything regarding the performance of the CW–BES in terms of
the removal of particular PhACs. However, it can be estimated that it will perform at parity with CWs
and BES since microbial degradation, plant uptake, and substrate adsorption will all take part in the
removal of PhACs (Hartl etal., 2021; Luo etal., 2023). Furthermore, it has significant advantages
over the other two systems because of its ability to produce electricity, recover nutrients, and handle
fluctuations in organic and hydraulic loading. Additionally, the operation and maintenance of the
CW–BES are not complicated. The schematic of a typical CW–BES and its applicability in various
aspects of sustainable wastewater management options has been depicted in Figure 2.4.
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29Occurrence and detection of pharmaceuticals in wastewater
2.9 SUMMARY
The PhACs are found in concentrations ranging from µg/L to ng/L in various aquatic
environments, such as wastewater, surface water, and even groundwater. Even at such low
concentrations, PhACs can significantly affect entire ecosystems. However, no legislation or
standards have been made yet due to the lack of availability of sufficient data for PhACs. The
reason behind the lack of data is the detection of such PhACs. PhACs require the use of high-
end instruments, such as LC, GC, LC–MS, GC-MS, MALDI-ToF, and others, for their detection.
Furthermore, the samples need to be properly collected, transported, stored, and analyzed for
their precise measurement. An important step in measuring PhACs having concentrations lower
than the detection limit of instruments is the use of SPE. The challenges in dealing with PhACs
do not end there. Most of the PhACs have a complex molecular structure, high hydrophilicity,
unfavorable dissociation constants, and other physicochemical properties that prevent them from
being removed using conventional treatment methods. Employing advanced treatment methods,
such as AOPs, membrane filtration, or adsorption, only increases the cost of treatment. Hence,
to remove these PhACs in a sustainable, cost-effective manner, the use of CW, BES, and CW–
BES has been explored, and it was found that CW–BES and CW have the potential to treat real
wastewater contaminated with such PhACs. Due to their ability to recover resources in the form
of nutrients and electricity, ability to remove soluble and insoluble organics, non-requirement
of mandatory pre-treatment, and efficiency in removing PhACs, CW–BES may be a probable
solution to tackle complex wastewater comprising of PhACs and other such recalcitrant organic
compounds. However, further studies on the up-scaling of these systems and modifications to
existing systems should be carried out to increase electricity generation, reduce HRT, and provide
higher treatment efficiency.
Figure 2.4 Schematic of CW, BES, and CW–BES and the favorability of the systems in terms of various aspects of
sustainable wastewater management option.
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30 Detection and Treatment of Emerging Contaminants in Wastewater
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© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0035
Bing Wang1,2, Tao Jiang2, Nana Wang2 and Qianqian Zou1
1College of Resources and Environmental Engineering, Guizhou University, Guiyang, Guizhou 550 025, China
2Key Laboratory of Karst Georesources and Environment (Guizhou Universit y), Ministry of Education, Guiyang,
Guizhou550025,China
ABSTRACT
Emerging contaminants (ECs) have received widespread attention globally due to their potential ecological and
human health impacts. Sludge, a byproduct of the sewage treatment processes, accumulates amounts of ECs
or toxic byproducts that have not been fully degraded. Without proper treatment, it may affect the resource
utilization of sludge and damage the ecological environment. Therefore, it is significant to investigate the generation
mechanism of ECs in municipal sewage/sludge and explore effective treatment technologies to remove them. This
chapter first reviews the main occurrence of ECs in municipal sewage/sludge. Secondly, the potential environmental
risks of ECs are evaluated, and the treatment technologies of different ECs are discussed in detail, such as anaerobic
consumption, aerobic composting, and advanced oxidation. Finally, suggestions and prospects are put forward for
the removal of ECs from municipal sewage/sludge.
Keywords: municipal sludge, emerging pollutants, treatment technologies, risk assessment, resource utilization
3.1 INTRODUCTION
With the progress of industry, agriculture, and urbanization, various emerging contaminants (ECs),
trad itional organ ic pollutants, and heav y metals have also emerged i n the environment, posi ng a serious
threat. Among them, ECs persist in the environment at low concentrations. Common ECs include
endocrine disruptors (EDCs), pharmaceuticals and personal care products (PPCPs), perfluorinated
compounds (PFCs), and disinfection by-products (DBPs) of drinking water and microplastics (Cheng
et al., 2021). ECs have attracted global attention due to their concealment, persistence, and complexity
in environmental governance. ECs can be directly discharged through various channels, such as
aquaculture sewage, domestic sewage, and industrial sewage, or degraded and treated by wastewater
treatment plants (WWTPs) before being discharged into the environment (Dubey et al., 2021). As
one of the essential places for treating ECs, WWTPs can still detect low concentrations of ECs in
the effluent after treatment. Therefore, discharging water containing trace amounts of ECs into the
Chapter 3
Emerging contaminants in municipal
sewage/sludge: occurrence, risk
assessment, and treatment
technologies
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36 Detection and Treatment of Emerging Contaminants in Wastewater
environment may cause secondary pollution of the aquatic environment. In addition, sludge is a
byproduct generated during the sewage treatment process, accumulating incompletely degraded ECs
or toxic byproducts. Suppose untreated or improperly treated sludge is directly applied as fertilizer to
soil or prepared into value-added products. In that case, it may indirectly cause harm to human health
through the food chain and limit the resource utilization of sludge. Therefore, how to efficiently degrade
ECs in sewage/sludge is of great significance for reducing ecological risks. This chapter systematically
summarizes the sources of ECs in municipal sewage/sludge, and evaluates the environmental risks
brought by ECs. At the same time, a detailed discussion is conducted on the treatment technology
and degradation mechanisms of ECs in existing sewage/sludge. Finally, suggestions and prospects for
removing ECs from sewage/sludge are proposed.
3.2 OCCURRENCE OF ECS IN MUNICIPAL SEWAGE/SLUDGE
The ECs originating from sewage are collected through the municipal system and flow to WWTPs.
Urban sewage is a type of mixed wastewater, including domestic sewage, industrial wastewater,
and surface runoff rainwater. The research results indicate that the removal efficiency of ECs from
sewage by WWTPs is only 30%, and most of the ECs were transferred to municipal sludge through
adsorption. Therefore, the concentration of ECs in municipal sludge may be higher after enrichment
than in inflow sewage. The sludge produced by WWTPs may cause serious environmental risks in
the subsequent resource utilization process (Barret et al., 2012). Municipal sludge can be used for
biogas production and as a raw material for biofuels, and it can also be digested and then used for soil
improvement in agriculture. However, the ecotoxicological effects of residual ECs in municipal sludge
on microorganisms, animals, and plants are currently a concern in this field. Hence, this section aims
to summarize the occurrence of ECs in municipal sewage/sludge and trace their possible sources. It
is helpful to well design the removal technologies of ECs in WWTPs. The primary sources of ECs in
WWTPs are summarized in Figure 3.1.
Antibiotics are widely used in multiple industries, such as healthcare, veterinarians, and
agriculture, and are also one of the most common ECs in sewage. However, most antibiotics are not
utilized by organisms and are released into the environment as parent compounds or metabolites.
The main sources of antibiotics in WWTPs are medical wastewater, domestic wastewater, and
aquaculture wastewater. The types of antibiotics used in the aquaculture industry mainly include
tetracyclines, sulfonamides, and quinolones. The amount of antibiotics discharged by this industry
far exceeds the total human use. For example, Zhi et al. (2020) investigated the pollution status
of veterinary antibiotics on household farms in the Erhai region of China. The results showed that
antibiotics were found in soil, wastewater, and feces, the content of antibiotics in feces was the highest.
Tetracyclines (mainly chlortetracycline) had the highest concentration (404.95 mg/kg) compared with
other antibiotics. The main types of antibiotics on chicken farms were quinolones and macrolides.
In addition to antibiotics, high concentrations of pharmaceuticals generated during production can
remain in pharmaceutical wastewater. However, pharmaceutical companies have limited wastewater
treatment capacity, resulting in many pharmaceuticals entering WWTPs. Furthermore, approximately
60–85% of pharmaceuticals are excreted from the body as raw compounds or metabolites through
feces or urine after ingestion and then enter the WWTPs.
Antibiotic resistance genes (ARGs) are typical ECs that have attracted attention due to their adverse
effects on treating pathogenic infections during antibiotic therapy. As the previous text shows, widely
used antibiotics cannot be completely metabolized by humans or animals, and residuals would be
discharged into the WWTPs. If low concentrations of antibiotics existed in the environment for a long
time, it could increase the probability of producing ARGs and promote their proliferation. Similarly,
the sources of ARGs in WWTPs are extensive, mainly from aquaculture, pharmaceuticals, hospitals,
household wastewater, and initial rainwater runoff (Qin et al., 2020). The urban drainage system enters
WWTPs by collecting the initial rainwater runoff, and ARGs in the septic tank of the breeding farm and
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37Emerging contaminants in municipal sewage/sludge
field irrigation enter WWTPs along with the rainwater runoff. The increased hydraulic load of WWTPs
may reduce the removal efficiency of ARGs. Garner et al. (2017) detected as many as 121 kinds of
ARGs in a single urban river sample, and five kinds of ARGs sul1, sul2, tet (O), tet (W), and erm (F) in
urban inland rivers were increased after a rainstorm under the same background value. However, the
complex composition of rainwater may promote the variation and proliferation of ARGs, while limited
research systematically elucidates the interaction between ARGs and rainwater components.
Natural and synthetic steroid hormones belong to a category of endocrine disruptors, causing
serious harm to the environment and humans, even in trace amounts. Natural steroid hormones, such
as progestogen, mineralocorticoid, androgen, and estrogen, are secreted by the human and animal
ovaries, testes, placentas, and adrenal cortex. The concentration of steroid hormones in sewage is
closely related to the composition and distribution of the population. Steroid estrogens in WWTPs
exist in inactive glucuronic acid glycosides, and sulfate complexes, or free forms. The source of steroid
estrogen in the pharmaceutical industry is by-products produced by preparing oral contraceptives,
which inflow WWTPs along with the sewage. According to a current study, the urine excreted by
males every day contained estrone (3.9 µg), 17β-estradiol (1.6 µg), and estriol (1.5 µg), while pregnant
women had a higher excretion quantity, reaching 600 µg estrogen, 259 µg 17β-estradiol, and 6000 µg
estriol (Johnson et al., 2000). In another study, Garner et al. (2017) detected the daily emissions of
12 natural estrogens in pig and cow urine. The results showed that the daily urinary excretion rates
of 12 natural estrogens in boars and sows ranged from 322.5 to 575.4 µg/d and 330.3 to 1100.7 µg/d,
respectively. The urinary excretion quantity of 12 natural estrogens in non-pregnant beef cattle ranged
from 338.2 to 2093.2 µg/d, the urine excretion quantity of pregnant beef cattle was 4974.9 µg/d, and
the total estrogen excreted by a male beef cow was 1201.1 µg/d. The natural estrogen in livestock urine
is the main source of estrogen in livestock wastewater, and the ecological risks of its discharge into
the environment should also be of concern.
Microplastics are a kind of EC inevitably produced in daily life. Their particle and fiber sizes are less
than 5 nm, characterized by their small volume and strong adsorption capacity. In the WWTPs, the
types of microplastics are mainly microfiber, microplastic fragments, and plastic particles. Currently,
Figure 3.1 Primary sources of ECs in WWTPs.
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38 Detection and Treatment of Emerging Contaminants in Wastewater
the main sources of microplastics in the W WTPs include personal care products, cosmetics, and laundry
textile fibers in domestic sewage, the breaking of large pieces of plastic in industrial wastewater, and
the plastic brought by rainwater runoff. Praveena et al. (2018) found the existence of microplastics in
all facial cleanser/scrub samples, mainly low-density polyethene and polypropylene. In another study,
Chang (2015) found that the bestselling facial cleanser in the United States was characterized by white,
opaque balls with particle sizes ranging from 60 to 800 µm. These microplastics were similar to the
color of plankton, and were easy to mistakenly eaten by fish, and were then transferred to a higher
trophic level through the food chain. This noteworthy finding raises significant ecological concerns
about the potential bioaccumulation and biomagnification of microplastics within aquatic ecosystems.
In addition, fiber microplastics mainly originate from washing daily clothes, rotor spinning, fabric
friction, and cutting in the textile process. The studies showed that the content of fiber microplastics in
the roughened textile was five times higher than that in the unprocessed textile, and the number of fiber
microplastics extracted from the traditional cut textile was 3–31 times higher than that of the laser cut
textile (Cai et al., 2020). Pinlova et al. (2022) systematically studied the existence of fiber microplastics
during yarn production. Fiber microplastics have always existed in yarn production, and the spinning
process parameters significantly affected the production of fiber microplastics, including ring spinning,
compact spinning, rotor spinning, and air jet spinning. A study found that the inflowing wastewater of
the WWTPs contained 15.70 (±5.23) microplastics/L, and 0.25 (±0.04) microplastics/L were detected
during emission. Even though a small number of microplastics were released per liter of water, many
microplastics would inflow into the environment due to the enormous amount of water treated.
Rainwater and sewage confluence exist due to unreasonable urban planning, and plastic wastes
may be carried in the surface runoff, forming microplastics through friction decomposition in the
flow process. Cheung et al. (2019) detected the microplastic abundance of Hong Kong rivers after
rainfall and obtained that the abundance of microplastics in the river after rainfall was 7.428/m3,
almost twice the observed value of coastal sea level in the same area. The microplastics transported
by discontinuous and explosive surface runoff would multiply during rainfall; thus, surface runoff is
also one of the sources of microplastics in WWTPs that cannot be ignored.
The ECs in municipal sludge originate from sewage, their content is positively correlated with
the concentration of ECs in the sewage, and adsorption is considered an essential mechanism for
transferring ECs from sewage to sludge. The current concentration range of ECs in sludge ranges from
ng/kg to mg/kg. The transfer of ECs from sewage to sludge depends on the physical and chemical
properties of ECs (Dubey et al., 2021). Li et al. (2013) detected the presence of 18 antibiotics in
sewage/sludge samples collected from 45 WWTPs in 23 cities in China, including seven quinolones,
six sulfonamides, and five macrolides. These sludge samples all showed similar antibiotic composition
characteristics, and there was a significant correlation between total organic carbon and the total
concentration of antibiotics. Besides, the types of ECs in sludge are closely related to the type of
sludge. Martín et al. (2015) found that nonsteroidal anti-inflammatory pharmaceuticals, estrogen,
and antiepileptic pharmaceuticals were more concentrated in the primary sludge, while antibiotics
β-recept or blockers and lipid modu lators had h igher concentr ations in t he secondar y sludge. Meanwhi le,
the concentration of ECs in sludge increased with the extension of sludge retention time. Positively
charged ECs were more beneficial to adsorption onto sludge, such as positively charged amitriptyline,
clozapine, verapamil, risperidone, and oxazine (Stevens-Garmon et al., 2011), but neutral compounds
only adsorb onto sludge by hydrophobic interactions. Differently, Ya n et al. (2014) reported that high
concentrations of quinolones in sludge were adsorbed onto sewage/sludge by chelating cations.
Various ECs have been found in sewage/sludge from global countries, and ECs in sludge are enriched
into sludge by adsorption, influenced by multiple factors. However, current studies mainly focus on
the interaction between ECs in wastewater and solid phases, and their relationships with colloids and
suspended solids are unclea r. Besides, although the analysis methods of ECs in sewage have been relatively
mature, the analysis methods in sludge are still lacking. It is urgent to establish standard analysis methods
to determine the abundance and types of ECs (such as microplastics and viruses) in sludge, analyze the
components of ECs in sludge, and reduce the risks to the ecological environment.
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39Emerging contaminants in municipal sewage/sludge
3.3 RISK ASSESSMENT OF ECS IN MUNICIPAL SEWAGE/SLUDGE
3.3.1 Ecological risk assessment
ECs usually have characteristics such as biological toxicity, environmental persistence, and
bioaccumulation, and their cumulative level and detection frequency in the environment are increasing
day by day. Consequently, it is imperative to assess the ecological risk associated with ECs in the
environment. The United Nations Environment Programme has explicitly stated that the impact of
ECs such as antibiotics and pharmaceuticals on aquatic ecosystems must be considered. Ecological risk
assessment is the process of predicting the likelihood of harmful effects of ECs on the ecosystem. It
refers to the risks borne by the ecosystem and its components, or the threat posed by uncertain accidents
or disasters within a certain area, such as an individual, population, community composition, or the
entire ecosystem. Ecological risk assessment, as a systematic analysis method, provides forward-looking
prevention strategies for protecting ecosystems. At present, the four-step method is commonly used for
ecological risk assessment based on dose–effect assessment and exposure assessment. Figure 3.2 shows
the basic steps of ecological risk assessment. Among them, hazard identification is to determine the
potential risk of pollutants to the ecological environment based on field research, data collection, and
risk source identification. Exposure assessment is based on hazard identification, accurately describing
the exposure intensity, exposure pathway, and spatiotemporal range of ecological receptors. Dose–effect
assessment is to analyze the possible ecological effects of ecological receptors exposed to a certain
risk source. Risk characterization is the combination of both exposure assessment and dose–effect
Figure 3.2 Basic steps of ecological risk assessment.
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40 Detection and Treatment of Emerging Contaminants in Wastewater
assessment to evaluate the risk and magnitude of stress factors on ecosystems and their components
and to analyze the uncertainty of the evaluation results (Wu et al., 2023; Yan g et al., 2022a).
The main purpose of ecological risk assessment is to integrate the relationship between exposure
assessment and effect assessment and then characterize the risk. There are two commonly used
expressions for risk characterization: qualitative and quantitative. When data and information
resources are sufficient, quantitative evaluation is usually used. Quantitative risk assessment methods
mainly include entropy method, safety threshold method, and probability method.
The entropy method is to compare the measured environmental concentration (MEC) or predicted
environmental exposure concentration (PEC) of pollutants in the water environment with the
maximum concentration, representing that the aquatic ecosystem is not endangered, and obtain the
risk entropy (RQ). That is RQ = PEC/PNEC. The PNEC value is usually the ratio of acute and chronic
toxicity data (lethal concentration half (LC50), effect concentration half (EC50), and maximum no effect
concentration (CNOE) to the assessment factor (AF). The corresponding risk levels were classified
(Ren etal., 2023) as shown in Table 3.1. Wu et al. (2023) used the entropy method to calculate 22 types
of PPCPs found in WWTPs and surface water and quantitatively allocate risks from specific sources.
The findings indicated that there were significant differences in the ecological risks of PPCPs from six
sources (medical sewage, farmland drainage, aquaculture, WWTPs, domestic sewage, and livestock
discharge), but none of them reached high risks. Among them, although domestic sewage poses the
most significant threat to the aquatic ecosystem, its contribution in terms of source proportion is lower
compared to that of medical sewage. The incidence of potential risks resulting from urban domestic
sewage (RQ > 0.01) is higher at 88.9% compared to rural domestic sewage at 75.9%. Camotti Bastos et
al. (2020) evaluated the potential ecological toxicity of pharmaceutical compounds in sewage/sludge
to the environment using the entropy method. The results showed that the RQ values of trimethoprim
(25.20), ciprofloxacin (8.98), and norfloxacin (7.55) against bacteria in lime sludge were higher than 1.
Additionally, the RQ values for sulfamethoxazole against invertebrates and algae in digested sludge were
32.47 and 46.70, respectively, indicating extremely high ecological risks. The entropy method is suitable
for evaluating the toxic effects of individual compounds and is relatively simple to apply. However, it
is only a rough estimation of ecological risks, which leads to uncertainty in its calculation results. For
example, the measured total amount is related to the actual intake of the organism, individual exposure
differences within the population, and sensitive differences (Thomaidi et al., 2016).
The safety threshold method characterizes the ecological risk of ECs by comparing the safety
threshold of biological communities with the exposure concentration of pollutants. The ratio
of the concentration at 10% on the cumulative distribution curve of species sensitivity or toxicity
data (SSD10) to the concentration at 90% on the cumulative distribution curve of environmental
exposure concentration (EXD90) is used to analyze the degree of overlap and characterize the risk,
that is, MOS10 = SSD10/EXD90. The safety threshold method utilizes both the distribution curve of
pollutant toxicity effects and the curve of pollutant environmental exposure concentration, which
is an extension of the entropy method. When MOS10 > 1, it indicates that there is no risk; when
MOS10 ≤ 1, it signifies a significant overlap between the two distributions, indicating that the pollutant
has the potential to pose a risk to the environment. Moreover, a smaller MOS10 value corresponds to
Table 3.1 Classification of ecological risk levels.
RQ Value Ecological Risk Levels
RQ < 0.01 Mild risk
0.01 ≤ RQ < 0.1 Low risk
0.1 ≤ RQ < 1 Medium risk
RQ ≥ 1 High risk
Note: The highe r the RQ value, the higher the ecologic al risk that t he pollutant poses to the environment.
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41Emerging contaminants in municipal sewage/sludge
a greater degree of overlap, indicating a higher ecological risk associated with the pollutant (He et al.,
2019). Liu et al. (2020) evaluated the ecological risk of tris (1,3-dichloro-2-propyl) phosphate (TDCPP)
using the safety threshold method. The findings indicated that both the toxicity data and exposure
data followed a normal distribution after logarithmic transformation. The resulting MOS10 value of
0.51 suggested that TDCPP has the potential to pose ecological risks due to its toxicity to growth
and development. The safety threshold method considers the uncertainty between environmental
exposure concentration and toxicity data and is a more reasonable risk assessment method. However,
when using the safety threshold method, it is necessary to use the cumulative probability distribution
map of logarithmic toxicity data. When a certain pollutant does not have sufficient toxicity data, this
method cannot be used for ecological risk assessment.
The probability method involves comparing the distributions of exposure concentration and
toxicity data concentration to determine the probability of the expected entropy value being greater or
less than the threshold value for determination. Specifically, Monte Carlo models were used to fit the
distribution of exposure concentration and toxicity data (Xu et al., 2015), followed by random sampling
of the two distributions (such as 10,000 samples) to determine the ratio of exposure concentration
to toxicity data and to obtain the probability of exceeding a specific RQ. The calculation formula
is: DBQ = EXD/SSD. The probability method lies in the determination of the actual exposure level
or probability curve of exposure concentration and toxicity reference values or toxicity parameter
probability curves. The actual exposure level or probability curve of exposure concentration is related
to the concentration of pollutants and their proportion of bioavailability and effects. The probability
curve of toxicity reference values or toxicity parameters is associated with the characteristics of
pollutants and ecological receptors, as well as the mechanism of interaction between them (Kooistra
et al., 2005). The probability method requires the collection of a large amount of data and information,
and the computational process is relatively complex. Its evaluation results have uncertainty, which
limits its use to some extent (Ren et al., 2021).
In summary, the entropy method can provide a relatively objective evaluation result, but it is
sensitive to the weight of indicators, and careful consideration should be given to indicator selection
and weight allocation when applying it. The safety threshold method can quickly evaluate specific
pollution events, but setting the threshold requires considering multiple factors, including risk
acceptance and uncertainty. The probability method requires high data requirements, reliable data
support, and consideration of uncertain factors. Therefore, to efficiently determine the risk level
of ECs in the ecological environment, multi-level risk assessment methods can be adopted in the
future, such as combining the entropy method and the probability method, and using various methods
and means to conduct ecological risk assessment from simple to complex, providing support for the
treatment of ECs in sewage/sludge.
3.3.2 Health risk assessment
ECs have been proven to interfere with the human endocrine system, affect the normal metabolism
and immune function of the human body, and then cause diseases. Environmental epigenome believes
that, in addition to chemical structure and concentration, ECs can lead to epigenetic changes through
DNA methylation and affect human health. To clarify the harm of ECs in sewage/sludge to human
health, there is a necessity for an objective health risk assessment of ECs in sewage/sludge. Predict the
estimated likelihood of adverse effects of ECs on the human body through health risk assessment, and
quantify the adverse effects on human health . To ensure a comprehensive health risk assessment, it is
essential to adhere to four key steps, which are hazard identification, exposure assessment, dose-effect
assessment, and risk characterization. Exposure assessment is the main basis of health risk assessment,
and the accuracy of exposure parameter data directly determines the reliability of health assessment
results. Exposure pathways include respiratory, dietary, and skin contact pathways (Hu et al., 2020).
Based on the carcinogenicity of pollutants, health risk assessment is categorized into two main
branches: carcinogenic risk assessment and non-carcinogenic risk assessment. In the evaluation of
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42 Detection and Treatment of Emerging Contaminants in Wastewater
ECs in sewage and sludge, non-carcinogenic risk assessment is commonly employed for health risk
assessment. The non-carcinogenic risk assessment is conducted by utilizing a risk index known as
the Hazard Quotient (HQ). The HQ is determined by dividing the long-term daily intake dose (CDI)
resulting from pollutant exposure by the reference dose (RfD). When HQ ≥ 1, it indicates that ECs
pose a high risk to human health; when HQ < 1, it means that ECs have a low health risk (Bruce et
al., 2010). Margenat et al. (2020) found that the concentration range of lincomycin, ciprofloxacin, and
azithromycin in lettuce leaves grown in sludge-improved soil was 0.7–4.2 ng/g, and its total risk index
(THQ) was less than 1, indicating that the level of antibiotics in lettuce was not a threat to human
health. Similarly, eating radishes would not result in adverse effects on human health, as indicated
by HQ values below 1 for azithromycin and sulfamethoxazole (You et al., 2020). Therefore, a human
health risk assessment of EC in sewage/sludge is important for the safe disposal of sewage/sludge
to clarify the extent of the risk to human health. Future health risk assessments should consider
the comprehensive impact of multiple factors, including environmental factors, lifestyle, and genetic
inheritance. Meanwhile, long-term follow-up research should also be implemented to better appreciate
the long-term effects of specific factors on human health through long-term observation and data
collection, which can help improve the scientific and practical nature of health risk assessment.
3.4 TREATMENT TECHNOLOGIES OF ECS IN MUNICIPAL SEWAGE/SLUDGE
3.4.1 Treatment technologies of ECs in municipal sewage
3.4.1.1 A d s o r pt ion
As a tr aditional sew age treatment technolog y, the adsorption method utilize s porous solids (adsor bents)
to adsorb pollutants onto the surface of the adsorbent, thereby purifying sewage. The commonly
used adsorbents are activated carbon, biochar, activated alumina, zeolite, and clay minerals. These
adsorbents usually have suitable pore size and surface structure and do not undergo chemical reactions
with the adsorbent or medium (Varsha et al., 2022). Among them, activated carbon (AC), as one of the
adsorbents, has been widely used due to its rich functional groups, strong stability, and good recovery
performance. It has been successfully used for the adsorption of ECs, such as perfluorooctanoic acid,
pharmaceuticals, antibiotics, and microplastics. Research reports that the different pore structures
and morphological characteristics of AC can affect the adsorption efficiency of target pollutants. For
example, AC with micropores (width <2 nm) can better adsorb small-molecule pollutants, while it is
generally difficult to achieve ideal adsorption effects for large-molecule pollutants. Therefore, Bedia
etal. (2018) increased the porous structure and surface area of AC by activating it with FeCl3, thereby
improving the removal of antipyrine. Xu et al. (2023) used S/Fe co-doping to activate AC, increasing its
specific surface area to 1194.14 m2g-1 and enriching its porous structure, the removal rate of triclosan
also reached 91.5%. Vieira et al. (2021) also found that activating AC through K2CO3 significantly
increased the porous quantity of AC and effectively removed atrazine. In addition, AC can be divided
into granular activated carbon (GAC) and powdered activated carbon (PAC) based on its appearance
and morphology. Generally, PAC has a shorter adsorption time and stronger adsorption capacity than
GAC. However, PAC may remain largely in activated sludge after use, making it difficult to recover
and separate, and it is usually used as a disposable adsorbent. Therefore, based on the characteristics
of the adsorbent and its regeneration cost, AC is still not considered the optimal adsorbent material,
and many pharmaceuticals cannot achieve good removal effects through AC.
The other adsorbent is clay minerals, a non-toxic, cheap, and natural mineral considered a good
adsorbent material. Currently, clay minerals are mainly used as adsorbents to remove antibiotics from
ECs. Their adsorption mechanisms mainly include ion exchange, electrostatic interaction, hydrophobic
interaction, and so on. Meanwhile, it was found that after modification treatment (heat treatment, acid
activation, chemical treatment), clay minerals can improve their specific surface area, biocompatibility,
and regeneration, and as well as their adsorption capacity for target pollutants. In addition, biochar, a
porous carbon-rich material prepared by pyrolysis under anaerobic conditions, has a longer life cycle than
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43Emerging contaminants in municipal sewage/sludge
activated carbon. Compared with other adsorbents, biochar has a relatively rich source, from agricultural
wastes, animal and plant residues, and urban waste, and is considered the most promising adsorbent
material. T he adsorption mecha nism of biochar on EC s in water mainly includes ele ctrostat ic interactions,
π-π interactions, and pore filling. Finally, pore filling is a unique pollutant removal mechanism of biochar
that is closely related to the microporous surface area of biochar. Besides, modification can further
improve the physical and chemical properties of biochar to enhance its adsorption capacity.
The th ree mater ials mentioned ab ove are curr ently commonl y used or the most pr omising ad sorbents,
and adsorbent materials such as silica gel, alumina, and zeolite also have certain application value
in practical environments. Although adsorption can easily and quickly remove pollutants, it cannot
currently be used as a large-scale sewage treatment method due to limitations in adsorption capacity,
cost, and regeneration performance. Therefore, the future research direction of adsorption methods
should be to develop cheaper and more efficient adsorbents.
3.4.1.2 Biological treatment
According to the treatment environment of sewage, biological treatment can be divided into aerobic
and anaerobic biological treatment. Among them, the activated sludge method in aerobic treatment is a
commonly used biological treatment process in WWTPs (Mpongwana & Rathilal, 2022). ECs adsorbed
into activated sludge are degraded or transformed through microbial metabolism. At the same time,
some ECs can also serve as a source of nutrients for microorganisms, promoting their metabolic
processes. The degradation processes of ECs through the activated sludge method mainly involve
hydroxylation, carboxylation, oxidation, and ring opening, leading to their degradation into H2O
and CO2. For example, tetracycline undergoes oxidation during biodegradation (Ta şkan et al., 2016).
Gemcitabine, cephalosporins, and penicillin antibiotics may undergo carboxylation reactions during
biodegradation (Kamal et al., 2023; Kong et al., 2019). Sulfonamide antibiotics undergo processes such
as hydroxylation and acetylation (Wang et al., 2023). However, considering that ECs mostly exist in
trace concentrations in the environment, the energy generated during the degradation process may not
be sufficient to sustain microbial life activities. This may require the addition of additional nutrients to
maintain the growth and metabolism of microorganisms. In addition, the degradation efficiency of the
activated sludge method is also affected by the characteristics of sludge, operating conditions, and the
complex properties of the ECs themselves. When the sludge index is high, it may cause sludge bulking,
reducing its ability to adsorb pollutants. The high or low pH of the solution and changes in water
temperature can affect the activity of enzymes, thereby affecting the biodegradation effect.
Anaerobic biological treatment refers to the decomposition of ECs into CO2 and CH4 under
anaerobic conditions and the combined action of multiple microorganisms. Compared with aerobic
processes, anaerobic processes have lower sludge production and operating costs. In recent decades,
many studies have been focused on the anaerobic depletion treatment of ECs. Some studies have found
that anaerobic biodegradation can reduce nitro, demethylation, and hydrolysis reactions, breaking
toxic ECs into simpler, less toxic small-molecule substances. However, some studies have shown that
most perfluorinated compounds are not biodegradable. This is attributed to the high polarity of C–F
bonds in perfluorinated pollutants, which increases the hydrophobicity and liposolubility of these ECs
and hinders the biodegradation process. The degradation mechanisms of other ECs through anaerobic
biological treatment mai nly include adsorption, non-biological reactions, and biodegradation. Di fferent
enzymes produced during microbial metabolism may affect the degradation effect of ECs during the
biodegradation process. For example, Carneiro et al. (2020) found that acidic enzymes may increase
their affinity for organic groups, thereby improving the removal rate of some ECs. Perfluorooctanoic
acid and perfluorooctane sulfonic acid achieved removal rates of 60% through acidic microorganisms
(Huang & Jaffé, 2019). In addition, peroxidase, nitroreductase, and cellobiose dehydrogenase also
affect the degradation effect. However, due to the high-cost limitations of biocatalysts in large-scale
applications and the possibility of some efflux of chemicals damaging enzyme activity. Therefore, it is
necessary to develop green, economical, and efficient remediation technologies in the future.
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44 Detection and Treatment of Emerging Contaminants in Wastewater
3.4.1.3 Advanced oxidation processes
Advanced oxidation processes (AOPs) change the structure of pollutants by generating strong oxidizing
free radicals (OH) and chain reactions, degrading them into small-molecule substances, and then finally
oxidizing them to CO2 and H2O (Jiang et al., 2023). Commonly used AOPs include photocatalysis,
Fenton oxidation, and ozone oxidation. These processes have been extensively applied to various ECs,
such as antibiotics, PPCPs, and perfluorinated compounds. Photocatalytic oxidation mainly involves the
degradation of pollutants through strong oxidizing free radicals generated by semiconductor catalysts
under ultraviolet/visible light. Photocatalytic degradation mainly undergoes the following processes: (1)
The pollutants are adsorbed on the surface of the catalyst. (2) The pollutants a bsorb suitable photons
and generate holes in the valence band. (3) The pollutants are degraded through a redox reaction under
the generated electron–hole pairs, and the H2O and O2 on the catalyst surface also generate hydroxyl
and superoxide-free radicals through the reaction, which indirectly degrade the pollutants. Common
photocatalysts include nanoprecious metals, metal oxides, and composite catalysts, and using different
photocatalysts can produce different degradation effects. For example, TiO2 has strong photocatalytic
ability and a low price, but its utilization range for visible light is small. Similarly, as another type of metal
oxide cat alyst, ZnO also exhibits excellent cat alytic per formance only u nder UV irradiation. Nonmetallic
photocatalysts such as graphene, organic semiconductors, and covalent organic frameworks have
attracted extensive research in the field of photocatalysis due to their good stability, suitable bandgap
width, and no metal leaching. The degradation pathways of ECs through photocatalytic oxidation can
be divided into three types: (1) The pollutants undergo photoisomerization before degradation. (2)
Under light, many reactive oxygen species are generated to oxidize and decompose pollutants. (3) Some
organic pollutants absorb photons to produce living oxygen substances and then degrade their excited
state. Table 3.2 lists the removal rates of ECs by some photocatalysts .
Ozone, as a strong oxidant, can directly or indirectly oxidize ECs. Direct oxidation is a selective
reaction between ozone molecules and electron-rich sites in ECs. The indirect reaction mainly involves
decomposing ozone into more reactive and less selective ·OH to oxidize ECs. Solid catalysts have been
used for heterogeneous catalytic ozonation reactions to avoid toxic by-products (such as bromate) that
may form during the ozone oxidation process. Solid catalysts have also been used to promote the
decomposition of more ·OH by O3. For example, LaCoO3 as a catalyst for ozonation degradation of
typical ECs, can improve the degradation performance of benzotriazole in individual ozonation and
reduce the production of toxic by-products (Zhang et al., 2019b). Cai et al. (2021) used CoFe2O4 as
Table 3.2 Removal rate of ECs by different photocatalysts.
Photocatalysts Target
Pollutants
Removal Rate
(%)
Reaction Time
(min)
References
C–N–S tridoped TiO2Tetracycline 99 180 Wang et al. (2011)
Multiwall carbon
nanotubes/BiOI
Antipyrine 100 120 Gao et al. (2020)
TiO2/g-C 3N4Diclofenac 93 90 González-González et al. (2022)
Bi2WO6Tetracycline 97 120 Chu et al. (2016)
β-FeOOH@g-C3N4Carbamazepine 92 30 Wang et al . (2020)
BiVO/CHCOO(BiO) Bisphenol A 99 180 Zhang et al. (2019a)
InS/GdO Oxytetracycline 80 50 Murugalakshmi et al. (2020)
ZnO-doped g-C3N4Ciprofloxacin 91.2 150 Van Thuan et al. (2022)
BiOBr/BiVO Organic dye 96 120 Liu et al. (2022)
SnO2/CeO2Tetracycline 97 120 Mohammad et al. (2021)
Mn-CCMN Crystal violet 97 120 Yang et al. (2022b)
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45Emerging contaminants in municipal sewage/sludge
a solid catalyst for catalytic ozonation, greatly improving the degradation rate of clofibric acid and
increasing the mineralization rate from 29.3% in a single ozonation to 72.7%. Pokkiladathu et al.
(2022) studied the AC/CeO2/ZnO catalyzed ozonation to remove bisphenol A from water, resulting
in a 25% increase in mineralization efficiency compared to non-catalytic ozonation. In summary,
using solid catalysts to catalyze ozonation can accelerate the oxidation reaction and generate more
unselective reactive oxygen species (·OH, 1O2, O2
i- and so on), thereby enhancing the degradation and
mineralization of pollutants. In addition, the coupling process of photocatalytic ozonation has also
been applied to the degradation of ECs, such as acetaminophen, antipyrine, and diclofenac. Due to
O3 being more electron-friendly than O2, more ·OH is generated, and the photocatalytic ozonation
significantly increases the oxidation rate of ECs.
Persulfate (PS) oxidation has been a hot research topic in recent years for AOPs. The PS process
mainly degrades ECs through SO4-. Compared with other free radicals, SO4- has a higher oxidation-
reduction potential and a wider pH tolerance range. SO4- also has non-selectivity and can directly
react with various ECs, but the reaction rate is lower when PS directly reacts with ECs. Therefore, it
is necessary to activate PS to improve its efficiency in removing ECs. Pirsaheb et al. (2020) compared
the removal rate of amoxicillin using PS alone and ultraviolet (UV)-activated PS and proved that
activated PS has a higher removal rate of pollutants. Mainly attributed to the UV activation of PS,
which leads to O–O bond breakage and produces two SO4-, thereby improving the removal rate of
ECs. In addition, ultrasonic activation of PS is also one of the commonly used methods, and ECs are
mainly degraded through the following two pathways: (1) Ultrasound causes the rupture of cavitation
bubbles, resulting in a high-temperature and high-pressure environment, which activates PS to degrade
ECs. (2) The high-temperature and high-pressure environment generated by the rupture of cavitation
bubbles decomposes water molecules into ·OH, thereby activating PS to degrade ECs. In addition,
some transition metals and their metal oxides have high activation ability for PS and are currently one
of the most commonly used methods for PS activation to produce SO4-. ECs can be degraded by metal
ions in a single homogeneous phase.
3.4.1.4 Membrane treatment
Membrane treatment is the separation and purification of a mixture through potential, pressure, and
concentration differences. According to the pore size of the membrane, it can be divided into four
categories (microfiltration, ultrafiltration, nanofiltration, and permeation). Among them, ultrafiltration
technology has removed various ECs with smaller pore sizes (pore sizes range from 0.001 to 0.02 µm).
For example, Shakak et al. (2020) synthesized a nanocomposite ultrafiltration membrane (polysulfone/
polyvinylpyrrolidone/SiO2) to evaluate for removal of amoxicillin. Due to the presence of SiO2, the
hydrophilicity, porosity, and membrane flux of the composite membrane were increased. With increasing
SiO2 nanoparticles from 0 to 4 wt%, the amoxicillin separation performance increased from 66.52%
to 89.81%. However, ultrafiltration technology may not be able to completely and effectively remove
certain ECs (pore sizes 100–1000 times larger than ECs). Microfiltration technology is a membrane
process driven by static pressure differences, utilizing the ‘screening’ effect of a mesh filter medium
membrane for separation. Nanofiltration technology is a membrane separation method that utilizes a
pressure gradient as the driving force. Due to the presence of charged groups on the surface of most
nanofiltration membranes, the removal mechanisms for ECs mainly include the charge effect and the
screening effect. Perfluorooctane sulfonic acid, as a persistent EC, is negatively charged in aqueous
solutions and can be effectively removed through nanofiltration technology. In addition, infiltration
technology is divided into two categories: forward osmosis (FO) and reverse osmosis (RO), and ECs can
achieve good removal rates through infiltration technology. Guo et al. (2020) fabricated a thermoplastic
polyurethane/polysulfone (TPU/PSF) composite membrane using electrospinning, and then loaded
UiO-66-NH2 particles onto the membrane. The results showed that the UiO/TPU/PSF forward osmosis
membrane achieved a retention efficiency of 99.64% for tetracycline. Another permeation technology,
RO, is a membrane separation technology that uses pressure difference as the driving force to separate
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46 Detection and Treatment of Emerging Contaminants in Wastewater
solvents from solutions, with a membrane pore size between 0.5 and 10 nm. Alonso et al. (2018) found
that RO ca n achieve a 99.96% removal effect of ciprofloxaci n. The mechani sms by which ECs are removed
through membrane technology mainly include electrostatic interactions, size exclusion, biodegradation,
and hydrophobic interactions. Some non-polar ECs are mainly removed by size exclusion and adsorption
onto the membrane surface, while polar ECs are mainly removed through biodegradation.
The urgent problem and challenge that membrane technology needs to solve is membrane pollution
and blockage. Due to the potential for performance degradation and shortened membrane lifespan
during long-term use, it may affect the degradation effect of ECs. Therefore, new membrane materials
need to be developed to address the shortcomings of traditional membrane technologies. For example,
Mendes et al. (2018) prepared the cellulose acetate silica-mixed ultrafiltration membrane with good
permeability, hydrophilicity, and mechanical strength. Zhao et al. (2018) studied the thin-film
nanocomposite forward osmosis membranes. The future membrane technology of ECs should develop
composite membranes with strong stability, a large surface area, and efficient electron transfer.
Meanwhile, the energy consumption generated by aeration should be reduced.
3.4.2 Treatment technologies of ECs in municipal sludge
It can be seen from Section 3.2 that ECs in sewage are enriched into sludge by adsorption, such as
polychlorinated biphenyls, endocrine disruptors, and microplastics. Due to the low biodegradability and
high persistence of ECs, they pose a greater threat than traditional organic pollutants. Effectively reducing
the concentration of EC in sludge is of great significance to the environment and humanity (Golet et al.,
2002). The main treatment technologies and advantages of ECs in sludge are summarized in Figure 3.3.
3.4.2.1 Aerobic composting
Aerobic composting is a technology that utilizes aerobic microorganisms to decompose organic matter
in sludge. It can achieve a harmless and stable treatment of sludge. Factors affecting the effectiveness
Figure 3.3 Treatment technologies and advantages of ECs in sludge.
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47Emerging contaminants in municipal sewage/sludge
of composting include composting fertilizer, composting conditions, microbial action, or the type
and initial concentration of ECs. The most critical influencing factor is the microbial activity. In
addition, when the concentration of ECs in sludge is high, the decomposition of organic matter can be
correspondingly delayed, and the composting efficiency and quality can also change. Different types of
ECs have different synthesis methods and physicochemical properties, which may lead to differences
in degradation effects. Generally, the removal rate of tetracycline, sulfa, and macrolide antibiotics by
compost is higher than that of quinolone antibiotics because most quinolone antibiotics are synthetic
compounds with complex str uctures and a re not easily affected by microorgani sms. Khadra et al. (2018)
used plant by-products and excess sludge for composting and found that ampicillin, clarithromycin,
lincomycin, tetracycline, or trimethoprim could be eliminated, but ofloxacin and ciprofloxacin did
not degrade well in this process. Furthermore, the study found that different types of sulfa antibiotics
in sludge had different removal effects under aerobic composting, and the degradation order was
sulfamethoxazole > sulfadimethoxine > sulfadimidine. Thermophilic conditions have a crucial
impact on the composting process. High temperatures can promote tetracycline and sulfonamide
antibiotics in sludge more effectively than low-temperature conditions. Finally, different composting
fertilizers also affect the process. Lin et al. (2017) found that compost using pig manure as a substrate
was more effective in removing sulfonamide antibiotics than compost using chicken manure. In
summary, composting has good application prospects in sludge reduction treatment and removing
ECs from sludge. However, the driving mechanisms of aerobic composting for the removal of ECs
from sludge have not been systematically explored, and further exploration is needed.
3.4.2.2 Anaerobic digestion
Anaer obic digestion m icroorgan isms decompose E Cs in sludge in an a naerobic envi ronment and conver t
sludge into high-value-added products. The process of anaerobic digestion primarily consists of four
stages: hydrolysis, acidogenesis, acetogenesis, and methanogenesis. Among them, the hydrolysis stage
is the most critical, where complex organic compounds in sludge are decomposed into glycerol, amino
acids, and monosaccharide small-molecule compounds. Therefore, a part of the ECs is removed during
hydrolysis, thus reducing the number of ECs in sludge. The factors affecting the anaerobic digestion
process include temperature and sludge types. Temperature can affect the activity of microorganisms.
There are certain differences in temperature between different seasons, resulting in changes in the
concentration of ECs and the abundance of microbial communities in sludge. When granular sludge is
subjected to crushing treatment, the distribution of microorganisms could be disrupted, causing direct
contact between microbial communities and ECs to suffer toxic effects, thereby reducing the treatment
efficiency of ECs. Importantly, when ECs exist in sludge, the anaerobic digestion process would be
subject to many disturbances, such as inhibition of biogas production and imbalance of the microbial
community, making ECs unable to be effectively degraded. For example, Liu et al. (2018) found that
the removal of tetracycline in sludge through industrial-scale anaerobic digestion was challenging,
with a total removal rate of less than 18%. Elevated concentrations of sulfamethoxazole exhibited
significant toxicity towards microbial communities, leading to inhibition of substrate utilization and
biogas production (Cetecioglu et al., 2015). Based on this, additional measures can be taken to reduce
the inhibition of ECs in sludge on microorganisms and improve anaerobic digestion performance.
Advanced anaerobic digestion is a commonly used method to improve anaerobic digestion
performance, including ozone oxidation, ultrasonic combined ozone oxidation, and the addition of
iron-based compounds. Ozone oxidation accelerates the decomposition of ECs and enhances the
utilization of ECs by microorganisms. During the ultrasonic treatment of sludge, the rupture of
bubbles can create high pressure, high temperature, and a strong shear force, which is very helpful
for ECs reduction in sludge. The coupling of ultrasound and ozone oxidation aids in enhancing the
generation of reactive oxygen species during ozone oxidation. This synergistic effect accelerates the
degradation of ECs while reducing their inhibitory impact on microorganisms. It is worth noting that
the addition of iron-based compounds affects the hydrolysis process of sludge, and iron is beneficial
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48 Detection and Treatment of Emerging Contaminants in Wastewater
to the occurrence of enzyme catalysis. The research showed that the antibiotics, with the exception of
ofloxacin, were effectively removed in the sewage sludge at a dosage of 1000 mg/L Fe0, 20 d of solid
retention time, and an antibiotic concentration of 20 μg/L, and Er ysipelotrichia, Verrucomicrobia,
Clostridia, Caldiserica, and Alphaproteobacteria of the class were dominated microorganisms in the
anaerobic digestion (Zhou et al., 2020).
The utilization of anaerobic digestion proves to be a successful and efficient means of treating
ECs present in sludge. However, multiple ECs are present in sludge, and there is a lack of sufficient
research on the synergistic and antagonistic effects of each EC. Although most of the ECs can inhibit
the methanogenesis process, a few ECs (such as azithromycin and cefalexin) may promote methane
formation under specific conditions, while the mechanisms of action are still unclear.
3.4.2.3 Advanced oxidation processes
AOPs are of interest for the removal of ECs from sludge due to their ability to produce highly oxidizing
reactive oxygen species. Among them, ozone oxidation is a commonly used AOPs for removing ECs
in sludge, promoting the desorption of ECs in sludge into the water, and reducing the difficulty of ECs
removal. The removal of ECs from sludge by ozone oxidation mainly includes the following processes:
(1) ECs are oxidized by ozone in wastewater. (2) ECs are desorbed and then oxidized by ozone. (3)
ECs are directly oxidized by ozone and combined with sludge. Marce et al. (2017) found a variety
of pharmaceuticals (ciprofloxacin, sulfamethoxazole, carbamazepine, diclofenac, and ibuprofen) that
existed in sludge had been removed to a certain extent after the addition of ozone. However, the removal
rate of pollutants depended on their transferred ozone dose ranges. In fact, when there are differences
in the transferred ozone dose ranges of ECs, their removal rates may go to two extremes. For example,
provided the transferred ozone dose range is 5 mg/g SS, the removal rate of ibuprofen is about 35–45%.
Nevertheless, if the transferred ozone dose range is 10 mg/g SS, the removal rate would reach 99%.
In recent years, AOPs based on calcium peroxide (CaO2) have been an emerging research direction
in sludge pre-treatment technology, simultaneously achieving oxidative wall breaking and alkaline
hydrolysis of sludge. Through water splitting, CaO2 dissolves and decomposes into H2O2,·OH, and
O2- species, thereby facilitating the degradation of ECs in sludge (Equations 1–5).
CaOHOCaO
HH
O222
22
+→ +() (3.1)
2CaO HO Ca OH O222 2
22
+→ +
() (3.2)
HO OH OH
22
+→⋅+
−
−
e (3.3)
HO OH HO OH
22
22
+⋅ →+
(3.4)
HO
OH
+
22
⋅→ +
− (3.5)
3.4.2.4 Other treatments
With the continuous progress of technology, in addition to the common technologies mentioned above,
hydrothermal carbonization and microwave technology can also remove ECs from sludge. Below
is a brief introduction to these two methods. Hydrothermal carbonization refers to the process of
hydrolysis, dehydration, decarboxylation, condensation, and aromatization of sludge into high-value-
added products (hydrothermal carbon) and a small amount of gas under appropriate temperature,
pressure, and pH. During this process, pathogenic bacteria and other microorganisms in sludge
are killed and ECs are removed, achieving sludge reduction and harmless treatment. In WWPTs,
sludge can better combine with ECs in wastewater through extracellular polymers. Therefore, adding
microbial cells with their cellular structures to sludge can release high-molecular-weight polymers,
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49Emerging contaminants in municipal sewage/sludge
which are combined to form complex extracellular polymers. Due to cellular polymers, extracellular
polymers can directly come into contact with ECs, making it easier for sludge to become colloids for
EC sedimentation treatment. Because there is a strong attraction between extracellular polymers and
ECs, effectively removing ECs from sludge. For example, a study showed that bisphenol A can bind
with extracellular polymers contained in sludge through hydrophobic interactions, thereby achieving
a higher removal rate of bisphenol A (Yan et al., 2019).
Microwave technology can evenly and quickly heat samples to decompose, regulate, and destroy
pathogens. Combined with chemical oxidation, this technology can also be used as an independent
pre-treatment process and potentially improve sludge decomposition. The chemical oxidants H2O2 and
PS are widely used in sludge disposal, and they can also be combined with microwave technology to
produce synergistic effects. Research has found that microwave/hydrogen peroxide and microwave/
persulfate technologies have certain effects on sludge dissolution, degradation of ECs in sludge, and
removal of pathogenic bacteria (Bilgin Oncu & Akmehmet Balcioglu, 2013).
3.5 CONCLUSION AND FUTURE PERSPECTIVES
ECs in municipal sewage/sludge have become an important ecological and public health problem.
This chapter reviews and analyzes their sources, risk assessment, and treatment techniques. ECs in
urban sewage/sludge originate from medical institutions, pharmaceutical industries, and PPCPs. ECs
entering the sewage/sludge through the municipal sewage networks pose potential ecosystem risks
and negatively impact human health. The risk assessment of ECs in sewage/sludge is based on the
ecological risk assessment framework. The focus is to identify the risk sources of ecosystems and their
components, quantitatively predict the probability of risk occurrence and its harmful effects, and
take corresponding control measures. Considering the removal of ECs in sewage/sludge, common
treatment technologies include adsorption, biological methods (aerobic composting or anaerobic
digestion), and advanced oxidation processes. Although positive results have been obtained in the
identification, risk assessment, and treatment technology research of ECs in sewage/sludge, there
are also new challenges that need to be addressed simultaneously, including but not limited to the
following:
(1) With the continuous improvement of water quality management requirements, the toxicity
testing of ECs should cover the entire life cycle of the tested species while considering regional
research. The selection of testing indicators should not only be a simple acute toxicity endpoint
but also require the addition of more sensitive testing endpoints.
(2) Currently, research focuses on evaluating specific single ECs, while multiple ECs and their
metabolites often coexist in actual environments. The mixture of ECs may have synergistic
or antagonistic effects on aquatic organisms, and the toxic effects generated by the combined
effects should also be a key aspect of risk assessment. Therefore, comprehensive evaluation
methods for multiple ECs and their metabolites should be thoroughly studied.
(3) There are many uncertainties in each risk assessment stage, such as screening of risk sources,
defining risk receptors, determining evaluation endpoints, and selecting risk assessment
methods. Especially for risk assessment methods, there is significant uncertainty in the
selection of evaluation factors, statistical methods or models, the setting of various elements
in simulated ecosystems, the construction of risk assessment models, and the determination of
parameters. Therefore, establishing uncertainty analysis methods and reducing risk assessment
uncertainty are important research topics for future risk assessment.
(4) Research has shown that multiple methods are available for reducing and removing ECs from
sewage/sludge. Biological treatment technologies, such as aerobic composting and bioreactors,
have proven effective in degrading and transforming pollutants. Physical and chemical
treatment technologies such as adsorption, oxidation, and membrane separation also show
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50 Detection and Treatment of Emerging Contaminants in Wastewater
potential. However, it should be noted that different ECs may require targeted treatment
methods, and by-products or conversion products may be generated during the treatment
process, requiring further research on their environmental behaviors and potential risks.
(5) Traditional treatment techniques have certain treatment effects on ECs, but considering the
limitations of a single process and removal efficiency issues. T herefore, it is inevitable to develop
integrated technologies for the efficient removal of ECs, such as coupling membrane bioreactors
with advanced oxidation processes or coupling membrane bioreactors with forward/reverse
osmosis.
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© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0055
Surya Singh*
Division of Environmental Monitoring and E xposure Assessment ( Water & Soil), ICMR – National Institute for Research in
Environmental Health, Bhopal 462 030, India
*Corresponding author: suryasingh.nireh@icmr.gov.in
ABSTRACT
Microplastics are newly emerged contaminants having a ubiquitous presence in almost every kind of environmental
matrix. Water is one of the most important reservoirs of microplastics, which also serves as an efficient medium for
the transfer of these particles to various abiotic matrices and biotic lives. As per recent research, microplastics in
water are an emerging public health issue that needs attention, and hence, suitable treatment methodologies are
needed to reduce the contamination potential of water/wastewater. Although conventional wastewater treatment
methods are able to remove microplastics to some extent, complete removal is challenging to date. Therefore,
new techniques are being explored, among which the use of bioinspired molecules, metal organic frameworks, and
biological materials is important. Further, the mechanical removal of microplastics through engineered micromotors
and chemical degradation through various techniques have also been investigated. While some of these techniques
are attractive and provide suitable solutions, their wide-scale applicability and cost-effectiveness are issues.
Moreover, the techniques that can be suitably incorporated into conventional wastewater treatment systems are
more preferred. Considering all these issues, this chapter will discuss the recent technological advances in the
removal of microplastics from wastewater.
Keywords: emerging contaminants, microplastics, removal techniques, treatment, wastewater
4.1 INTRODUCTION
Microplastics are one of the emerging contaminants that are found to be present in almost all kinds
of environmental matrices, such as water, soil, air, snow/glaciers, etc. (Singh etal., 2022). Apart from
that, microplastics are also found in various food items, sewage/wastewater treatment plants, landfill
leachates, and so on (Acarer, 2023; Conti etal., 2020; Egea-Corbacho etal., 2023; Makhdoumi etal.,
2021; Sekar & Sundaram, 2023). The global presence of these microplastics in a variety of matrices is
primarily a result of inappropriate disposal and management of plastic waste. Accumulation of plastic
waste in the environment for a long time results in the breakdown of larger particles into smaller
Chapter 4
Recent advances in treatment of
microplastics in wastewater
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56 Detection and Treatment of Emerging Contaminants in Wastewater
pieces, resulting in microplastics (Liu etal., 2023). In order to be defined as microplastics, the size
of the plastic particles should lie in the range of 1 µm–5 mm (Frias & Nash, 2019). These small-size
plastic particles are able to invade biotic species, including humans, through ingestion and inhalation,
which poses a serious threat to the health of living beings. The presence of plastic particles has already
been reported in various fish, animal, and plant species (Hariharan et al., 2021, 2022; Veen etal.,
2022; Yu etal., 2021); and also in human blood, lungs, placenta, semen, urine, and so on (Jenner etal.,
2022; Leslie et al., 2022; Pironti etal., 2023; Ragusa etal., 2021; Zhao et al., 2023). Consequently,
genotoxic and cytotoxic impacts have also been reported (Cobanoglu etal., 2021; Kaur etal., 2022).
Therefore, the effective management of microplastic particles is essential.
Microplastics primarily originate through two different means – the first mode is their intentional
manufacture in the defined size range for various applications (known as primary microplastics),
such as in cosmetics, pharmaceutical industries, and daily-use products (viz., toothpaste, shaving
creams, shampoo, moisturizers, scrubs, etc.) (Osman et al., 2023); second mode of microplastics’
origin (known as secondary microplastics) is the breakdown of large-size plastic material/plastic
waste in the environment upon the action of various biotic and abiotic agencies (Osman etal., 2023;
Singh etal., 2021a). Between these two, the second mode of microplastics’ origin contributes more
(69–81%) to the environment and therefore calls for the appropriate disposal of plastic waste (EU,
2018; Singh etal., 2022). As far as the fate of microplastics is concerned, primary microplastics do
find their way into our daily lives for various reasons and then become part of the sullage or domestic
sewage, which is ultimately directed towards the sewage treatment plants (STPs) (Koyuncuoglu &
Erden, 2021). Similarly, industrial effluent with varying amounts of plastic waste, depending on the
type of industry, finds its way into effluent treatment plants (ETPs) (Umar et al., 2023). Secondary
microplastics, on the other hand, reach the water bodies through direct disposal of plastic waste in the
aquatic bodies, illegitimate discharge of effluent from industries, leaching and percolation of leachate
from municipal or hazardous dumpsites/landfills, and so on (Koyuncuoglu & Erden, 2021).
As a significant amount of microplastics reaches the STPs and ETPs, it is essential to have an
effective removal system for this contaminant (Ridall etal., 2023). Moreover, since these treatment
plants provide an environment where microplastics can breakdown into smaller pieces at a faster
rate owing to the presence of various chemicals and microbial moieties, the resulting microplastics
become more fragmented and smaller. Thus, it makes microplastics more prone to adsorbing various
contaminants, such as metals, chemicals, pigments, microbes, and so on, making these particles more
pernicious (Gao etal., 2023). Therefore, efficient removal of microplastics in various treatment plants
is crucial. However, as of date, there is no mechanism in these units for the targeted removal of
microplastics (Patil etal., 2023). The conventional treatment units help to remove some amount of
microplastic, but efficiency needs to be improved. For understanding the removal of microplastics,
STPs and ETPs may be clubbed into one unit, namely, wastewater treatment plants (WWTPs). In this
chapter, the details of various treatment processes for W WTPs will be outlined. The efficiency and
limitations of these processes will also be discussed. Further, major emphasis would be laid on the
advanced technologies in the field of microplastics’ removal from wastewater.
4.2 CHALLENGES IN THE MICROPLASTICS REMOVAL
The removal of microplastics from wastewater becomes challenging owing to various factors. Among
them, some of the factors are the different sources of origin of microplastics, the varied size range
(1 µm–5 mm), and the different shapes such as fibers, foam, granules, fragments, pellets, and so
on. The variable chemical composition of various microplastic particles also sometimes makes it
challenging to adopt any single technology (Lu etal ., 2023). The chemical composition of microplastic
particles may be of several types, but the majority of the particles are composed of polyethylene
(PE), polypropylene (PP), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polystyrene
(PS), polyamide (PA), polyester, nylon, polyacrylates, and so on (Singh etal., 2023). It is noteworthy
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57Recent advances in treatment of microplastics in wastewater
to mention here that a specific industry may discharge any particular composition of microplastics;
however, mixing effluents from a number of industries in the common effluent treatment plants results
in the mingling of different types of microplastics. Further, microplastic particles are not wholesome
plastic materials; rather they also contain a significant amount of chemicals in the form of additives
and plasticizers, which are generally mixed during their manufacturing process (Hahladakis et al.,
2018). Moreover, these particles also serve as an efficient vector for various contaminants occurring
in the environment, such as heavy metals, chemicals, microbes, and so on (Singh & Bhagwat, 2022;
Upadhyay etal., 2022). Thus, the removal of microplastics becomes crucial considering their inherent
as well as associated hazardous chemicals.
4.3 OVERVIEW OF CONVENTIONAL TREATMENT TECHNIQUES AND SHORTCOMINGS
Any conventional wastewater treatment process involves mainly three-step treatment, namely,
primary, secondary, and tertiary. Based on the technologies involved at each of these stages, the
removal efficiency keeps improving from primary to tertiary treatment. The efficiency of different
treatment steps evaluated by researchers is given in Table 4.1. Primary wastewater treatment generally
involves physical mechanisms to remove dirt, suspended particles, and various other solid materials.
At the initial level, different-size screens are applied, which grab the solid materials. This is basically
an exclusion process based on size. Screening is then followed by sedimentation. The basic principle
involved here is the suspension of wastewater in an idle position for a certain specified duration so
that heavier particles may settle down owing to the gravitational force. The efficiency of the primary
step specifically for microplastic removal ranges from 50 to 98% (Sun etal., 2019). It is notable here
to mention that the shape of the microplastics does affect the efficiency, as fiber-shaped particles
are removed more compared to fragments (Magnusson & Noren, 2014; Ziajahromi etal., 2017). The
limitation of this treatment process is that it cannot remove plastic particles with micrometer and
nanometer sizes.
The secondary step of the WWTPs generally involves biological treatment using attached growth
systems (e.g., trickling filters and rotating biological contactors) or suspended growth systems
(e.g., activated sludge processes, aerated lagoons, aerobic digestion, etc.). Further modifications in
the attached growth systems involve the development of moving-bed biofilm reactors (MBBRs).
Similarly, suspended growth systems involve the development of sequencing batch reactors (SBRs)
and membrane bio-reactors (MBRs). It has been reported that approximately 88% of the microplastic
removal may be achieved once the water undergoes a secondary treatment process (Sun etal., 2019).
Lares etal. studied the removal of microplastics in conventional activated sludge processes as well
as in advanced MBR systems. Upon comparison of both systems, it was concluded that conventional
systems resulted in approximately 1 microplastic particle per litre of effluent, while MBR technology
reduced this amount to 0.4 microplastic particle per litre of effluent (Lares et al., 2018). Though
this removal efficiency is significant, the remaining amount of microplastics in the effluent is finally
discharged into surface water bodies. Thus, WWTPs have become one of the most important sources
of microplastic pollution in the aquatic environment.
The ter tiary step provides another higher deg ree of treatment for the wastewater, generally involving
filtration and disinfection. Talvitie et al. compared the microplastics’ removal efficiency of different
tertiary-level treatments of WWTPs, viz. disc filter, rapid sand filtration, and dissolved air flotation
(Talvitie etal., 2017). Along with these, the efficiency of MBR in treating primary effluent was also
compared. It was found that 99.9% of the microplastics could be removed through MBR technology.
Moreover, the removal efficiencies of disc filter, rapid sand filtration, and dissolved air flotation lied in
the range of 40–98.5%, 97%, and 95%, respectively. The highest removal efficiency of MBR technology
among all the studied methods was attributed to the smallest pore size of membranes (0.4 µm) used in
MBR. However, there is scope for microplastics’ presence in the effluent even after tertiary treatment.
On average, tertiary treatment can enhance microplastic removal by up to 97% (Sun etal., 2019). At
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58 Detection and Treatment of Emerging Contaminants in Wastewater
first instance, it might appear that up to 97% treatment efficiency is good enough for the removal of
microplastics. However, it is to be understood that even 1% of microplastics per liter of treated water
discharged will result in millions of microplastic particles in the environment, considering the amount
of wastewater treated in WWTPs. Therefore, treatment methods need to be much more efficient.
4.4 ADVANCED TECHNIQUES FOR REMOVAL OF MICROPLASTICS
Considering the amount and risks imposed by microplastics, researchers are attempting to develop
advanc ed techniques t hat can ens ure their comple te removal fr om WWT Ps (Table 4.1). The se technique s
may be clubbed into physical, chemical, biological, and miscellaneous techniques (Figure4.1).
4.4.1 Physical techniques
4.4.1.1 A d s o r p t i o n
The adsorption process is one of the most important physical means of removal reported for
microplastics. Adsorption refers to the entanglement and diffusion of plastic particles onto a surface
through various forces, such as hydrogen bond/electrost atic/π–π interactions, and so on. A sponge-type
surface made up of graphene oxide and chitin has been synthesized and employed for microplastics’
removal. By using this, an efficiency of as high as 90% could be achieved for virgin polystyrene (Sun
etal., 2020). Another low-cost adsorption material, viz. biochar, made up of bio-based materials, has
also been synthesized. Basically, biochar is a type of charcoal that can be synthesized by pyrolysis of a
variety of feed materials, such as biowaste, cattle litter, crop residues, and so on. (Abuwatfa et a l ., 2021).
Therefore, it is character ized by a porous struct ure rich in carbon content. Removal of m icropla stics has
been studied using biochar synthesized from corn straw and hardwood. This biochar was integrated
with the filtration system of the WWTP to assess the change in removal efficiency. It was found that
efficiency increased from 60 to 80% to more than 95% through this biochar integration (Wang etal.,
2020a). Siipola etal. synthesized steam-activated porous biochar from the bark of coniferous trees,
viz. pine and spruce. This biochar was used for the removal of polyethylene microplastics of different
shapes. The shapes of the particles included spheres, beads, cylindrical fiber, and fleece fiber. It was
found that the removal efficiency of biochar varied for different shapes of particles. While 100%
removal was achieved for cylindrical and fleece fibers, beads and spheres were not removed completely.
This difference was attributed to the entanglement of different shapes of microplastics with biochar
(Siipola et al., 2020). Another study carried out modifications into the biochar surface properties
through the addition of iron nanoparticles. A comparison was made between the unmodified biochar
and iron-modified biochar, and it was deduced that microplastics’ removal efficiency increased from
75% to 100% upon integration of iron (Singh etal., 2021b). Moreover, the pH of the solution was found
to have no effect on the iron-modified biochar adsorption properties. Similarly, magnesium/zinc-
modified biochar was also used for the adsorptive removal of polystyrene microplastics, and efficiency
up to 99.5% could be achieved (Wang etal., 2021).
4.4.1.2 Filtration
Filtration is the process of physical removal of microplastics from wastewater by creating a barrier
using a membrane. Ultrafiltration membranes (pore size 1–100 nm) have been used for removing
microplastics (polyethylene) by Ma et al., and it was found that removal efficiency increased from
13% to 91% (Ma et al., 2019). Generally, filtration processes are applied in combination with
other water treatment processes, such as sedimentation and coagulation. Reverse osmosis (RO) is
another technique through which particles are captured through the application of semi-permeable
membranes. Ziajahromi etal. reported the performance of RO employed in a WWTP. It was reported
that even after the RO process, few microplastic fibers remained in the effluent (Ziajahromi et al.,
2017). It was deduced that it might be due to some defects, either in the membrane or in the supply pipe
system. The performance of polycarbonate, cellulose acetate, and polytetrafluoroethylene membranes
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59Recent advances in treatment of microplastics in wastewater
Table 4.1 Removal methods of microplastics.
Process Description Major Mechanism Lowest Size of
Microplastic
Particle Removed/
Finest Mesh
Efficiency (%) Advantages Challenges References
Wastewater
treatment plant
processes
Skimming, settling
of the entrapped
microplastics
300 µm99.9 Conventional
process, no
additional cost
Not possible to
remove MPs of size
<300 µm
Magnusson
and Noren
(2014)
Wastewater
treatment plant
processes
Primar y, secondary,
and tertiary 100 µm99.9 Conventional
process, no
additional cost
Not possible to
remove MPs of size
<100 µm
Carr etal.
(2016)
Wastewater
treatment plant
processes
Secondary
treatment 20 µm95.6 MBR process
exhibited greater
overall efficiency
Complete retention
is not possible
Michielssen
etal. (2016)
Tertiary treatment 97. 2
MBR 99.4
Wastewater
treatment plant
processes
MBR 250 µm99.3 MBR process
helped to retain
more microplastics
compared to
conventional
activated sludge
process
Not possible to
remove MPs of size
<250 µm
Lares etal.
(2018)
Al and Fe salt Coagulation <0.5 mm 45.34 ± 3.93 Simple process,
does not require
additional set-up
Low efficiency Ma etal.
(2019)
Adsorption using
biochar
Morphologically
controlled
mechanism (stuck,
trapped, and
entangled)
10 µm>95% Low cost and
efficient
Process is slow
and results in
obstruction of the
pores with time,
costly, regeneration
is tough
Wang etal .
(2020a)
Adsorption using
steam-activated
porous biochar made
up of the bark of
coniferous trees
Retention in the
surface pores >10 µm∼100% Low cost and
efficient for particles
>10 µm
Not possible to
remove MPs of size
≤10 µm
Siipola etal.
(2020)
≤10 µmCould not
retain
(Continued)
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60 Detection and Treatment of Emerging Contaminants in Wastewater
Table 4.1 Removal methods of microplastics (Continued).
Process Description Major Mechanism Lowest Size of
Microplastic
Particle Removed/
Finest Mesh
Efficiency (%) Advantages Challenges References
Adsorption and
thermal degradation
using:
Electrostatic
interaction and
chemical bonding
interaction
1 µmLow cost, eco-
friendly, and efficient
Stable performance,
keeping the
efficiency intact
even after 5 cycles of
adsorption-pyrolysis
Efficiency
decreases in
alkalescent
condition, in
water having high
chemical oxygen
demand, and in
presence of anions
such as H2PO4−
Wang etal .
(2021)
Magnetic biochar 94.81%
Mg modified
magnetic biochar
98.75%
Zn modified
magnetic biochar
99.46%
Filtration with GAC
(combined with
coagulation and
sedimentation)
Physical properties
(size and shape) 1–5 µm56.8–60.9% Efficient to remove
plastic particles of
nano-size range
Process is slow
and results in
obstruction of the
pores with time,
costly, regeneration
is tough
Wang etal .
(2020b)
Pulse clarification
with filtration
Entrapment in
sludge blanket
formed due to
coagulation floats
<100 µm85% Removal efficiency
is comparable to
the other treatment
plants having
advanced processes
Complete retention
is not possible
Sarkar etal .
(2021)
Bioinspired
molecules
Mechanical capture
mechanism driven
by the hydrophobic
and van der Waals
interactions
— — Flexible, possibility
to remove different
types of plastic
particles in
wastewater stream
Method yet to be
established for
practical purposes
Herbort and
Schuhen
(2017)
Photocatalytic
micromotors
Phoretic
interaction and
shovelling/pushing
interactions
— — Self-propelled devices,
works efficiently
independent of the
fuel
Selectivity of
micromotors for
microplastics is
crucial
Wang etal .
(2019)
Zr MOF-based
foams
Entrapment —95.5 ± 1.2% High performance,
excellent durability
Flexibility and
robustness of
MOF-based foams,
removal efficiency
affected by the
particle size and
zeta potential
Chen etal .
(2020)
(Continued)
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61Recent advances in treatment of microplastics in wastewater
MOF (MIL-100
Fe) nanoparticles
incorporated into
polysulfone matrix
Membrane
separation 40 µm— Removal of MPs
(PE and PVC) from
textile wastewater
Tested for only
textile wastewater
Gnanasekaran
etal. (2021)
Photocatalytic
degradation
Photocatalysis
using n-TiO2
semiconductor
MPs extracted
from commercial
exfoliating scrub
Max. mass
loss of 6.4%
Environment-
friendly technology
High cost,
requirement of
specific set-up
Ariza-
Tarazona etal.
(2019)
Algal degradation Electrostatic charge
on the microplastic
particles and algal
surfaces
20 µm94.5% No chemical,
electrical, and
mechanical
operations
Efficiency will
vary owing to
physiological and
topographical
differences on the
seaweed surface
Sundbæk
etal. (2018)
Fungal degradation Biodegradation — — Biological
process, no toxic
side-products
Study investigated
only low-density
polyethylene.
Method yet to be
established for
other polymers
Kunlere etal.
(2019)
Bacterial
degradation
Biodegradation —50–61% Biological
process, no toxic
side-products
Method yet to be
established for
wide variety of
polymers
Rajandas etal .
(2012)
Electrocoagulation Charge
neutralization,
flocculation
— 90 (pH 3–10)
99.24 (pH 7.5)
Does not rely
on chemicals or
microorganisms,
energy efficient
Operation time
needs to lowered
down
Perren etal.
(2018)
Combinatorial
method
Electrocoagulation,
electroflotation,
and membrane
filtration
MPs collected from
WWTPs filtered
through mesh dia
26 µm
100% Short retention time,
high efficiency
Application of
pressure creates
additional cost,
Membrane rupture
results in high
replacement
frequency
Akarsu etal.
(2021)
Adapted from Singh etal. (2021a).
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62 Detection and Treatment of Emerging Contaminants in Wastewater
was also evaluated for the removal of polystyrene and polyamide microplastic particles (size range of
20–300 µm). More than 94% of mass removal efficiency could be achieved from all three membranes
(Pizzichetti et al., 2021). However, major disadvantages of membrane technology are fouling and
abrasion with time.
4.4.1.3 Agglomeration and sol–gel process using bioinspired molecules
A new concept of bioinspired molecules has been proposed for the possible removal of microplastics
(Herbort & Schuhen, 2017). This concept involves the agglomeration of microplastics facilitated
through silicone-based chemicals in a water-induced sol–gel process (Herbort et al., 2018), thus
combining the attributes of both physical and chemical techniques. Since microplastics are small
particles that remain scattered in the aquatic system, agglomeration thereof helps in size enhancement,
making the trapping of these particles easier (Sturm etal., 2023). Sturm etal. studied the removal of
microplastics in a WWTP and compared the efficiency of three mechanisms, viz. advanced oxidation
process (AOP), granular activated carbon (GAC), and GAC combined with organosilanes. It was found
that individual mechanisms of AOP and GAC could not result in significant removal of microplastics;
however, reduction reached up to 61% upon connecting the organosilane molecules in series with
the GAC (Sturm etal., 2023). The principle involved here was the chemical binding of organosilanes
with microplastics through the sol–gel process, resulting in three-dimensional agglomerates. These
agglomerates can then be easily skimmed from the water. The polarity of the microplastic polymers
plays an important role here, as non-polar polymers (e.g., polyethylene and polypropylene) are easier
to remove compared to polar polymers (e.g., polyvinyl chloride and polyamide). Further, the effects of
temperature and water composition were also studied. It was found that variation in temperature and
water composition does not affect the removal of microplastics through the agglomeration-fixation
reactions of organosilanes (Sturm etal., 2021).
Figure 4.1 Illustration of advanced techniques for removal of microplastics from wastewater.
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63Recent advances in treatment of microplastics in wastewater
4.4.1.4 Micromotors
Micromotors are one of the recent developments in the field of environmental remedial applications,
which are basically a combination of physical and chemical processes. These micromotors are energy-
driven devices in which their motion direction can also be controlled (Zhang e t al . , 2 017). Micromotors
have been found to be useful for the removal of a variety of pollutants, such as dyes (Zhang etal.,
2017), oil (Mou etal., 2015), heavy metals (Villa etal., 2018), suspended matter (Wang et al., 2019),
and so on. Considering their efficacy, researchers have applied micromotors for microplastics removal
as well (Wang et al., 2019). In this case, photocatalytic micromotors were designed to make them
self-propelled under ultraviolet (UV) light illumination. The propulsion was made possible due to
the photocatalytic reactions taking place in the particles, viz. TiO2. These photocatalytic reactions
involve the creation of conduction band electrons and valence band holes, which ultimately lead to
fluid flow in the direction of propulsion. Wang etal. showed that micromotors help in the removal of
microplastics through two mechanisms, viz. phoretic interactions and shoveling. Phoretic interactions
result in the collection and simultaneous travel of microplastic particles along with the micromotors,
thus resulting in their removal. On the other hand, shoveling involves the removal of a large number
of microplastic particles through a moving assemblage of magnetic catalytic particles. This magnetic
assemblage was constituted by the interaction between the magnetic nickel layers inside the core-shell
structure of Au@Ni@TiO2 micromotors (Wang etal., 2019).
4.4.2 Chemical techniques
4.4.2.1 Metal organic framework (MOF)-based moieties
MOF-based moieties have been in use for various environmental applications, such as air pollution
control (Zhang et al., 2016), water contaminants removal (Kobielska et al., 2018; Mon et al., 2018),
volatile organic carbon removal (Vikrant etal., 2020), and so on. Considering their wide-scale utility,
researchers have employed MOFs for microplastics’ removal as well (Chen eta l ., 2020). Gnanasekaran
etal. synthesized hydrophilic MOF, viz. MIL-100 (Fe) nanoparticles, which were incorporated into
a polysulfone matrix to design a composite membrane. This MOF-incorporated membrane was
successfully utilized for the removal of microplastics in textile wastewater (Gnanasekaran etal., 2021).
This membrane also performed well for a range of microplastics’ concentrations without losing its
permeability. Another study reported the synthesis of zinc-based MOF for the removal of microplastics
(Dongyu etal., 2022). It was developed by cultivating the zeolitic imidazolate frameworks (ZIF), viz.
ZIF-8, on the wood aerogel. The efficiency for removing the polystyrene particles of size 90–140 nm
was reportedly 86% using ZIF-8@Aerogel. The removal efficiency of this MOF was attributed to the
strong electrostatic interaction between negatively charged microplastics and positively charged MOF
(Dongyu etal., 2022). Similarly, the removal of polystyrene microplastics was also reported using the
MOF material ZIF-67 (Wan et a l ., 2022). In this study, the adsorption ratio of polystyrene microplastics
to ZIF-67 reached approximately 92% with an equilibrium time of 20 min. Moreover, apart from
electrostatic interactions, hydrogen bond interactions and π–π interactions were also reported to be
significant in the microplastics’ removal mechanism (Wan et a l ., 2022). In a recent study, another MOF
structure was reported to remove microplastics along with other dissolved contaminants from water
(Haris et al., 2023). This nano-pillared structure was synthesized by growing the two-dimensional
MOF on the core-shell-structured carbon and FeO (C@FeO) nano-pillars. The advantage of adding
FeO to the structure was obtained by developing magnetic properties. Moreover, this structure had
a high surface area and ample active sites for the adsorption process. Approximately 100% removal
efficiency was achieved through this MOF structure for microplastics’ removal (Haris etal., 2023).
4.4.2.2 Advanced oxidation processes
Advanced oxidation processes (AOPs), such as the Fenton reaction, photocatalysis, persulfate
oxidation, photolysis, and so on are some of the most suitable methods for the mineralization of
various recalcitrant organic contaminants (Santos etal., 2023). Reactive oxygen species (ROS), such
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64 Detection and Treatment of Emerging Contaminants in Wastewater
as hydroxyl radical (•OH), sulfate radical (
SO
4
i
−
), superoxide (
O2
i
−
), and so on are usually employed
to mineralize a variety of organic moieties. Therefore, microplastic degradation was also studied
using single- as well as hybrid-AOPs (Kim et al., 2022). Ariza-Tarazona et al. demonstrated the
photocatalytic degradation of polyethylene microplastics in an aqueous and solid matrix using the
n-TiO2 semiconductor (Figure 4.2). The degradation was estimated by the weight loss (Ariza-Tarazona
et al., 2019). Similarly, Tofa et al. used zinc oxide nanorods for the photocatalytic degradation of
low-density polyethylene (LDPE) residues (Tofa etal., 2019). The degradation was confirmed by the
increased brittleness and the presence of cavities, wrinkles, and cracks on the surface of LDPE after
the photocatalysis. The degree of degradation was found to be directly proportional to the catalyst
surface area. Some investigators also used ozone (O3) and O3/H2O2 and reported the degradation
and removal of microplastics up to 99.2% (Hidayaturrahman & Lee, 2019). Easton et al. reported
polyester microfiber degradation using UV/H2O2 with mass loss efficiency of 52.7% after 48 hours of
reaction (Easton etal., 2023).
4.4.3 Biological techniques
4.4.3.1 Algal degradation
Researchers have shown that algal masses affect the nature of microplastics in the environment and
thus may help in their removal. Algae either degrade the polymer matrix biologically or alter the
density of the polymer particle, resulting in a change in its floatation behavior (Priya etal., 2022).
Sundbæk et al. reported that polystyrene microplastics get sorbed on marine microalgae, namely,
Fucus vesiculosus, with an efficiency as high as 94.5% (Sundbæk e tal ., 2018). The alginate compounds
released from the cell walls of the microalgae further assist in the sorption of microplastics. Adsorption
of polystyrene microplastics has also been studied on the green alga – Chlorella, Scenedesmus, and
Pseudokirchneriella subcapitata (Bhattacharya etal ., 2010; Nolte etal., 2017). The mechanism of this
interaction between the microplastic particles and algal cells was attributed to the electrostatic charges
on the surface. It was deduced that positive and/or neutral charges on the surface of microplastic
particles show greater affinity towards the algal cells (Bhattacharya etal., 2010; Nolte et al., 2017).
Further, blue-green algal species such as Oscillatoria subbrevis and Phormidium lucidum have also
been found to degrade polyethylene plastics (Sarmah & Rout, 2018). The fundamental requisite for the
degradation of plastics through the algal community has been identified as the formation of biofilms
over the surface of polymers. With the advancement in the field of biotechnology, some genetically
modified algae have also been produced, which help in degrading microplastics. For example,
Chlamydomonas reinhardtii was modified to produce ‘polyethylene terephthalate hydrolase’ in order
to degrade polyethylene terephthalate films and terephthalic acid (Kim etal., 2020).
Figure 4.2 Schematic representation of photocatalytic degradation of microplastic particles.
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65Recent advances in treatment of microplastics in wastewater
4.4.3.2 Fungal degradation
Fungi are known to be tolerant to a variety of chemicals, metalloids, metals, and so on owing to their
ability to produce various extracellular enzymes and/or bio-surfactants that can efficiently breakdown
polymers into monomeric units (Straub etal., 2017). Fungi also help in catalyzing the oxidation of
aromatic/non-aromatic substances, owing to the production of lignin-degrading enzyme ‘laccase’
(Straub et al., 2017). This ability of fungi may be utilized to degrade microplastic polymers as well.
Genera that can perform the degradation of common polymers (such as polyethylene, polypropylene,
and polyethylene terephthalate) include Aspergillus, Penicillium, Cladosporium, and so on since
these utilize microplastic particles as the only source of energy (Oliveira etal., 2020). Kunlere etal.
recently reported that Mucor circinelloides and Aspergillus flavus can efficiently breakdown low-
density polyethylene (Kunlere etal., 2019).
4.4.3.3 Bacterial degradation
Bacterial degradation of plastic polymers was reported long ago in 1993, when a consortium of bacteria
was used to degrade polypropylene (Cacciari etal., 1993). Since then, a number of bacterial species
have been isolated from a variety of habitats that possess the potential for plastic degradation (Awasthi
et al., 2020). It has been seen that bacteria generally develop an efficient enzymatic mechanism to
degrade microplastics for survival in polluted habitats. These bacterial enzymes usually increase the
hydrophilicity of microplastic particles, thus converting them into alcoholic or carbonyl residues. Such
bacteria can be used to degrade microplastics in other habitats as well. Degradation of low-density
polyethylene within two months of incubation has been reported in the presence of Microbacterium
paraoxydans and Pseudomonas aeruginosa, with efficiency as high as 61% and 50.5%, respectively
(Rajandas etal., 2012). Similarly, polypropylene-degrading bacterial strains include Chelatococcus,
Bacillus, Pseudomonas, and so on, which were obtained from areas contaminated with plastics
(Anand etal., 2023). Bacterial enzymes that were found to be substantial for microplastics degradation
include lipases, laccases, esterases, lignin peroxides, manganese peroxides, and so on. Recently,
bacterial cellulose hydrogels have been used as potential bioflocculants for trapping microplastics
(Mendonca etal., 2023). Microplastics were found to be adsorbed as well as embedded in the fibrillar
and porous gel-like hydrogel, which resulted in flocculation. A total flocculation rate of 88.59% could
be achieved at the optimized conditions of temperature, immersion time, and hydrogel:microplastics
ratio (Mendonca etal., 2023).
Bacterial degradation generally involves physico-chemical alterations in the polymers, such as
polymer chain length reduction, polymeric functional group alterations, and so on which helps to
degrade polymers through their enzymatic action. However, the major drawback of this method is its
extremely slow rate of degradation. Further, in order to minimize the formation of any noxious end-
product after the bacterial degradation process, it is considerable to involve a consortium of bacteria
(Singh & Wahid, 2015).
4.4.3.4 Constructed wetlands
Constructed wetlands are one of the most cost-effective and efficient wastewater treatment techniques,
which involve naturally occurring geochemical and biological processes to treat the wastewater
(Parashar et al., 2022). Microplastics removal through constructed wetlands has recently been
identified (Long et a l., 2023; Rozman e t al., 2023). In one of the studies, fibers and bead-shaped
microplastic particles were introduced into the wetland system with Iris vegetation. A hydraulic
retention time of four days was provided for microplastics. Upon testing the effluent, it was found
that only 0.296% and 0.003% of the total microbeads and fibers, respectively, were present in the
effluent. Moreover, longer fibers were comparatively retained more in the wetland system compared
to smaller fibers (Rozman etal., 2023). Multi-combination and multi-stage constructed wetlands were
also utilized for estimating the microplastics’ removal efficiency. It was found that a combination
of systems can efficiently trap a considerable amount of microplastics. Vertical flow, horizontal
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66 Detection and Treatment of Emerging Contaminants in Wastewater
subsurface flow, and surface flow types of constructed wetlands resulted in 25.71%, 32%, and 23.53%
removal of microplastics, respectively (Long etal., 2023).
4.4.4 Miscellaneous techniques
4.4.4.1 Electrochemical methods
Electrochemical methods are used for the removal of a variety of pollutants from water and wastewater.
Electrocoagulation is a technique in which direct current is supplied to the anode and cathode. As
electrodes make contact with water, metal gets oxidized and releases ions into water, resulting in
the formation of agglomerates along with the impurities settling at the bottom of the tank, which
can be removed later. In the electroflotation process, these agglomerates float at the top of the tank.
Electrodecantation is another process that involves the phenomena of gravity as well as electrodialysis.
These processes are efficient as well as environment friendly since they do not involve the addition of
chemicals. Commonly used metal ions for the electrocoagulation process are Fe2+ and Al3+. In a study
conducted by Perren e tal ., Al3+ ions were utilized in the electrocoagulation process for the removal of
sphere-shaped polyethylene particles (Perren etal., 2018). The obtained removal efficiency was more
than 90%. Moreover, the highest removal was found at a pH of 7.5.
4.4.4.2 Nanotechnological methods
Kang et al. employed the combination of oxidation and hydrolysis of microplastics over carbon
nanotub es (CNTs). In this st udy, ma nganese car bide nanopart icles were encapsu lated in nitr ogen-doped
CNTs using the pyrolytic method. This synthesized material was then used for peroxymonosulfate
activation (for producing ROS) and microplastics’ mineralization under the hydrothermal condition.
The outcome demonstrated that up to 50% removal of microplastics could be realized using this
method (Kang etal., 2019).
4.4.4.3 Combinatorial methods
Akarsu et al. used a combination of electrocoagulation, electroflotation, and membrane filtration
techniques for the removal of polyethylene and polyvinyl chloride microplastics from wastewater
(Akarsu et al., 2021). The electrode combination of Al–Fe was found to be optimal at a pH of 7
and a current density of 20 A/m2. The membrane used was a polyvinylidene fluoride microfiltration
membrane w ith a pore size of 0. 22 µm. W ith this com bination, 100% remova l efficiency for micr oplastics
could be achieved.
Wang etal. employed the chemical coagulation process with sedimentation and filtration using
GAC for microplastics’ removal in water treatment plants (Wang eta l ., 2020b). When coagulation was
combined with only sedimentation, only 40–54% removal efficiency could be achieved. Nevertheless,
larger-sized microplastics could be removed more efficiently using coagulation–sedimentation
compared to smaller-sized microplastics. However, upon integrating GAC filtration in the treatment
chain, 57–61% of microplastics’ removal could be achieved. Further, GAC filtration enhanced the
removal of smaller-sized microplastics (1–5 µm) up to 74–98%. Similar findings were reported
by Zhang et al. after exploring the removal efficiency of the combined processes of coagulation/
flocculation, sedimentation, and granular filtration. Without the granular filtration process, the
efficiency was not enough to remove micro- as well as nanoplastics. However, upon adding filtration
after the sedimentation, efficiency increased from 87% to almost 100%, especially for the particle size
range of >100 µm (Zhang etal., 2020).
4.5 FUTURE PERSPECTIVES
Literature shows the possibility of removing microplastics through various techniques; however, there
is still a long way to go. Since WWTPs receive microplastics of mixed size, shape, and composition,
and the removal techniques employed in various WWTPs are also different, performance comparison
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67Recent advances in treatment of microplastics in wastewater
among different techniques becomes challenging. Moreover, from sample collection to the final
analysis and identification of microplastics, uniformity is also required in procedures. Therefore, one
of the most important aspects of future research in the area of microplastics’ removal is to develop a
consensus over universally accepted defi nitions and unifor m analytical procedures. Fur ther, it has been
seen across the studies that PE, PP, PVC, PET, and PA are the most common types of microplastics in
the WWTPs. Therefore, removal mechanisms for these polymers need to be focused on. Another area
that requires attention is the monitoring of microplastics of size less than 1 µm (viz., nanoplastics).
Owing to the limitations of instrumentation techniques, smaller-sized microplastics are often left out
of analytical identification. Apart from this, it is also important to target the microplastics present in
sludge. Usually, microplastics trapped in the WWTPs result in their accumulation in the sludge, which
poses a risk for the soil and groundwater contamination in the long run. Therefore, future studies
should also take into account the removal of microplastics from the sludge produced from WWTPs.
4.6 CONCLUSION
Efficient removal of microplastics from wastewater is critical in order to ascer tain the quality of natural
water reservoirs (surface/ground), as effluent is ultimately discharged into freshwater resources after
treatment. As of date, conventional wastewater treatment procedures do not involve any specific
mechanism to remove microplastics; rather, this contaminant gets removed simultaneously with other
organic and inorganic contaminants in wastewater. However, considering the increasing concern
over the microplastics’ presence in the treated effluent and their repercussions on human health,
advanced treatment methods need to evolve.
In this chapter, various advanced wastewater treatment techniques developed so far have been
discussed. These techniques offer significant potential to reduce the microplastics’ concentration in
the treated effluent. Nevertheless, operational cost, practical applicability, efficacy for most of the
types of microplastic particles, and energy efficiency need to be explored and improved further in the
advanced techniques.
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© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0073
Nikita Yadav1, Ashootosh Mandpe2* and Sudeep Shukla3
1Amity School of Earth and Environmental Sciences, Amity University Haryana, Gurugram 122 413, India
2Department of Civil Engineering, Indian Institute of Technology Indore, Indore 453 552, Madhya Pradesh, India
3Environment Pollution Analysis Lab, Bhiwadi, Alwar 301 019, Rajasthan, India
*Corresponding Author: Dr. Ashootosh Mandpe, Assistant Professor, Department of Civil Engineering, Indian Institute of
Technology Indore, Indore 453 552, India
*Corresponding author: as_mandpe@iiti.ac.in
ABSTRACT
Inappropriate disposal of pharmaceutical waste containing antibiotics into water bodies developed the catastrophe
of antibiotic resistance. The occurrence and, thereafter, bioaccumulation of antibiotics in the aquatic ecosystem
have raised concern about their associated toxicity toward aquatic organisms. Their presence in aquatic bodies has
been widely discussed in developed nations. However, in many developing countries like India, minimal research
has been reported on the status of antibiotics in the aquatic environment. This chapter summarizes the global
distribution of antibiotics in the aquatic environment, their effects on the microbial community, the evaluation
and assessment of antibiotic risks, and the source tracking of these emerging pollutants. Another key objective of
this chapter is to investigate the trends in consumption, distribution, and fate of major antibiotic classes in India
and their dynamic relation to the biotic world. The eco-toxicity of these emerging contaminants towards different
flora and fauna communities at different trophic levels with targeted assessment and remediation technologies,
including percent removal efficiencies, has been discussed. Legislative and regulatory measures carried out for the
effective management of this growing epidemic by various governments have also been discussed.
Keywords: antibiotics, antibiotic resistance genes, bioaccumulation, emerging contaminants, remediation
5.1 INTRODUCTION
Mankind has witnessed a paradigm shift in the pathogenic/microbiological world after the sudden
discovery of penicillin by Alexander Fleming in the 1920s. Among the most significant achievements
of the 20th century was the discovery of antibiotics, which are produced by microbes. Several
microorganisms produce these metabolites, which can kill or delay the onset of further microbial
growth and development. This property of antibiosis provided them with a significant tool to
conquer the epidemic world by reducing mortality and morbidity for many significant diseases
Chapter 5
A brief account of the antibiotics
and antibiotic resistance genes in an
aquatic environment
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74 Detection and Treatment of Emerging Contaminants in Wastewater
(Nkoh et a l.,2023). Considerable growth has been reported in pharmaceutical industries (Aitken,
2020), which also gave rise to a dramatic increase in the utilization of antibiotics, not only for humans
but for animal husbandry practices too. The dumping of antibiotics in the aquatic waterways due to
improper handling and disposal from pharmaceutical industries, municipality runoff, hospitals and
dispensaries runoff, and effluent from animal husbandry practices led to the growing traces of these
emerging contaminants (ECs) into the environmental matrices. Both lentic and lotic water bodies face
the dilemma of antibiotic resistance due to the pseudo-persistent nature of these ECs (Wang etal.,
2023). This puts the ecosystem and healthcare services in a compromising position. Different aquatic
bodies with different levels of accumulation have other effects on the existing micro-communities of
flora and fauna, that is, they have adverse effect s on the micro-biomes of humans as well as physiolog ical
aberrations in the plant world. The lakes and ponds (i.e., lentic) system offers an essential setting for
studying the fate of antibiotics and the haulage of antibiotic resistance genes (ARGs) with a diverse
variety of niche areas, such as bacterial populations and associated floral and faunal communities
(Dong et al., 2022). Due to the low hydraulic coefficient, the lentic system is likely to succumb to
the accumulation of these new-age contaminants (Zhang et al., 2023). Hydraulic properties led to
the effective dispersal of pollutants among the water bodies. Since lentic system has a quantitatively
higher freshwater portion than lotic system, previous ones have a higher bioaccumulation factor and
serve as a standing reservoir for acquiring new resistances among the microbes of human interest.
Antibiotics are chemically complex substances with several functional moieties in their molecular
structure that belong to different specific classifications (Table 5.1) based on their non-selective mode of
action and their wide range of potential. Their varied and unique chemical structure provides them with
lipophilicity (Gevao etal ., 2022). The presence of specific functional groups gives them a peculiar feature
for targeting specific bacterial genomes. Since bacteria have labile and less stable genetic materials, it
aids them in overcoming the hindrances posed by antibiotics. Antibiotics can be resisted by microbes
through a wide variety of their associated metabolic strategies. Spontaneous mutations in prokaryotic
genomes lead to antibiotic resistance epidemic with horizontal gene transfer (HGT) (Deng etal., 2020).
The evolution of AR processes accumulated by adaptive and malignant microbes involves Darwinian
factors, that is, alterations occurring in antecedent functional genes of the prokaryotic genome, chosen
by selective environmental stressors. Due to selection processes, the defensive mechanism has been
reported in transportation systems such as efflux pumps, mutations in intracellular proteins like porins
that affect bacterial cell porosity, and barriers to these drugs’ entry. The lateral transmission of genes for
antibiotic resistance from source organisms is accelerated by adjustment to the evolutionary pressure
of antibiotics (Grenni et a l., 2018). When confronted with the antibiotics generated, bacteria within
the same ecosystem may modify their innate mechanisms – for example, by over-expressing efflux
systems, they introduce new pathways through HGT, that is, the transduction of heterologous genes, the
resistance mechanism from the producers (Lupo etal., 2012) (Figure 5.1).
Other varied genetic materials and mobile genetic elements are ubiquitous in aquatic bodies, such as
integrons, phages, transposons, a nd plasmids, which help acquire new resistances by serving as platforms
for gene aggregation and transmitting it to other microbes of human interest by subsequent mixing.
Henceforth, aquatic life was impacted, from the micro to macro level, as these chemicals bioaccumulated
at trophic levels. Bioaccumulated concentrations ultimately pass onto human consumption via the
supplies of veggies and fruits irrigated by such contaminated recycled water, dairy products, and water
drinking supplies, resulting in Multi Drug Resistance (MDR), as shown in Figure 5.2.
Based on pre-finding studies, the possible sources or occurrences, their fate, exposure to drinking
water, possible assessment of human health risk, removal by available treatment methodologies, and
regulatory preventive measures are taken into account in this study.
5.1.1 Antibiotics as emerging pollutants
The inception of rapid industrialization and altered patterns in consumer goods led to the emergence
of a new class of pollutants in the different environmental matrices. New-age contaminants are
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75A brief account of the antibiotics and antibiotic resistance genes in an aquatic environment
Table 5.1 Characteristics of different antibiotic classes.
S.
No.
Type of Abs
(Interest, 2020;
Map etal., 2020;
Moore, 2016)
Category Discovery
(Interest,
2020)
Common Examples Mode of Action (Map
etal., 2020; Moore, 2016)
Toxicity (Moore, 2016)
01. β-lactams Bactericidal and
broad spectrum
1928 Penicillin, amoxicillin,
cephalosporin
Interfere with the synthesis
of peptidoglycan layer of
cell wall of bacteria
Hypersensitivity,
hemolytic anemia
02. Sulfonamides Broad spectrum
and bacteriostatic
1932 Prontosil, sulfadiazine,
sulfisoxazole
Inhibiting the bacterial
synthesis instead of killing
them
Thrombocytopenia
03. Aminoglycosides Bacteriostatic Early 1940s Streptomycin,
kanamycin, neomycin
Inhibit the synthesis of
protein in bacteria
Nephrotoxicity,
ototoxicity
04. Tetracyclines Broad spectrum
and bacteriostatic
Late 1940s Doxycycline,
tetracycline,
oxytetracycline
Inhibit the protein
synthesis, so as the growth
and reproduction
Hepatotoxicity, tooth
discoloration, impaired
growth
05. Chloramphenicol Broad spectrum
and bacteriostatic
Late 1940s Levomycetin,
Chlornitromycin,
chloromycetin
Inhibit the protein
synthesis, so as the growth
and reproduction
Aplastic anemia, gray
baby syndrome
06. Macrolides Bacteriostatic 1950 Erythromycin Same as lactams but target
more number of species
than lactams
Coumadin interaction
07. Glycopeptides Bactericidal Late 1950s Vancomycin (drug of
last resort), teicoplanin
Inhibit bacterial cell wall
synthesis
Red man syndrome,
nephrotoxicity, ototoxicity
08. Oxazolidinones Broad spectrum
and bactericidal
Late 1970s Linezolid, cycloserine,
posizolid
Inhibiting the protein
synthesis at P-site of
ribosomal subunit 50S
Pharmokinetic profile
with low toxicity
09. Ansamycins Bactericidal and
narrow spectrum
Late 1950s Rifamycin, isoniazid Inhibit the production of
RNA, anti-viral activity
reported
Metabolic acidosis,
hematological disorders
10. Quinolones Bactericidal and
broad spectrum
Early 1960s Ciproflaxacin,
levoflaxacin,
travoflaxcin
Inhibits replication and
transcription of DNA
Phototoxicity, impaired
fracture healing, Achillies
tendon rupture
11. Streptogramins Narrow spectrum
with bacteriostatic
properties
Early 1960s Quinupristin
dalfopristin
Streptogramins A & B
synergistically inhibit cell
growth
Gastrointestinal
disturbance
12. Lipopeptides Bactericidal 1987 Daptomycin, surfactin Multiple cell- membrane
functions in bacteria
Low toxic and high
biodegradability reported
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76 Detection and Treatment of Emerging Contaminants in Wastewater
artificial or naturally present compounds that are not regularly detected in the ecosystem but possess
the propensity to infiltrate and have documented or anticipated harmful environmental consequences
and health impacts. Examples include compounds like pharmaceuticals, personnel care products,
corticosteroids, pheromones, flame retardants, insecticides, hormone-disrupting substances,
cleansers, lingering organic pollutants (the dirty dozen), and so on (Stefanakis & Becker, 2015).
Pharmaceutical compounds, especially antibiotics, have been identified as emerging contaminants
across the globe. Based on people’s consumption, these chemicals tend to be present in water bodies
as conventional treatment facilities are unable to remove them effectively. However, their detection in
the environmental matrices can be attributed to recent advancements in sophisticated analytical tools
and techniques that can quantify them at trace levels. Further sections evaluated the consumption
trends in antibiotic usage worldwide, particularly in India.
5.1.2 Occurrence of antibiotics and ARGs in water bodies
According to research that is presently accessible, the levels of antibiotics present in rivers and
streams, aquifers, and improperly disposed wastewater are generally within the acceptable range of
0.05–0.1 µg/L, as presented in Table 5.2. However, these concentrations can be identified with the
course of evolution in analytical techniques such as Liquid Chromatography Mass Spectrometry (LC-
MS), High Performance Liquid Chromatography (HPLC), and so on (Danner etal., 2019).
The possible significant pathways and hotspots for the contamination of aquatic bodies reported
in various studies with high anthropogenic activities are: effluents from wastewater treatment plants
Figure 5.1 Antibiotic resistance mechanism through different pathways: efflux pumps, alteration of cell wall
proteins, plasmid transfer, mutational events in the bacterial genome, and activation of antibiotics-degrading
enzymes.
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77A brief account of the antibiotics and antibiotic resistance genes in an aquatic environment
(WWTPs), which include household usage and municipal runs; pharmaceutical manufacturing plants
(Kumar etal., 2020); and animal husbandry practices, which include poultry and shrimp farms; and
aquaculture, as shown in Table 5.2. The utilization of antibiotics in livestock farming creates a conduit
for these substances to enter adjacent aquifers and waterways, as these are persistent and enter the
environment either by direct effluent discharge or from the excretory pathway, as shown in Figure 5.2
(Gray etal., 2019). Unused antibiotics, which are discarded in garbage, end up in landfills and finally
in the soil (Marathe etal., 2016).
It has become w idely accepted t hat the broad ex pansion of A RGs imposed by t he improper applica tion
of antibiotics poses a severe threat to the well-being of people and the environment. Wastewater
treatment facilities (WWTFs) encounter sewage comprising not merely antibiotics but also ARGs,
which can develop into an epicenter for the dissemination of ARGs and associated bacteria since they
provide favorable circumstances for bacterial development and have a higher selective constraint for
the dissemination of ARGs among various bacterial genera. Numerous ARGs have been identified to
date in samples connected to WWTFs, including wastewater influent prior to remediation and effluent
despite sterilization. WWTFs serve as important repositories for the numerous pervasive and widely
distributed ARGs found in ecological soil, water, and other ecosystems.
ARGs have been detected in WWTPs around the world. WWTPs are an important point source of
antibiotics and ARGs, as they receive and treat wastewater from households, hospitals, and industries.
Studies have shown that the concentration and diversity of ARGs in WWTPs can vary depending
on factors such as the type of treatment technology used, the size of the plant, and the source of the
wastewater. For example, the presence of sub-inhibitory concentrations of antibiotics in WWTPs can
select for antibiotic-resistant bacteria. Some studies have found that WWTPs that receive wastewater
from hospitals or animal farms have higher concentrations of ARGs compared to those that treat
mainly domestic wastewater.
Figure 5.2 Lifecycle analysis and processes associated with the fate of antibiotics.
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78 Detection and Treatment of Emerging Contaminants in Wastewater
Table 5.2 Trend of antibiotics consumption in the global context.
S.
No.
Continents Country-
wise Location
Antibiotics Type Concentration
(µg/L)
References
River/Lake/TTP
01. AFRICA Ghana (i) Ampicillin
(ii) Ciprofloxacin
(iii) Erythromycin
(iv) Sulfamethoxazole
Hospital waste
water effluent
and river water
0.027
11.35–15.73
7.9 4 –10.61
7.194
Azanu etal.
(2018)
Kenya (i) Sulfamethoxazole
(ii) Ciprofloxacin
(iii) Trimethoprim
Nairobi River 13.8
0.509
2.650
Ngumba
etal. (2016)
South A frica (i) Ampicillin
(ii) Ciprofloxacin
(iii) Nalidixic acid
WWTP influent
and effluent
6.57–8.92
27.1
25.2–29.9
Agunbiade
and Moodley
(2016)
02. AMERICA USA (i) Ampicillin
(ii) Cloxacilin
(iii) Erythromycin
(iv) Oxytetracycline
(v) Sulfadimethoxine
(vi) Sulfathiazole
Poudre R iver,
WWTP (influent
and effluent),
ground water
1.969
1.993
0.18
0.07–1.34
0.24–15
0.08
Cha etal .
(2006);
Lindsey
etal. (20 01);
Kolpin etal .
(2002)
Argentina (i) Monensin
(ii) Lascolid
(iii) Salinomycin
Del Plata
hydrological
basin
0.288–4.67
—
1.150
Alonso etal.
(2019)
03. ASIA India (i) Trimethoprim
(ii) Ciprofloxacin
(iii) Enrofloxacin
(iv) Norfloxacin
(v) Ofloxacin
(vi) Lomefloxacin
Patancheru
Enviro Tech
Ltd. Treatment
plant undiluted
effluent,
Karnataka
4.4
14000
210
25
55
8.8
Fick etal .
(2009)
Bangladesh (i) Trimethoprim
(ii) Sulfadiazine
(iii) Sulfamethiazine
(iv) Penicillin
Finfish
aquaculture
0.041
0.017
0.011
0.007
Hossain
etal. (2017)
Iraq (i) Levofloxacin
(ii) Amoxicillin
(iii) Ciprofloxacin
WWTPs (raw
water)
0.177–0.414
1.50
1.270–1.344
Mahmood
etal. (2019)
China (i) Chlortetracycline
(ii) Doxycline
(iii) Enroflaxacin
(iv) Erythromycin
(v) Sulfadiazine
(vi) Tetracycline
Filtered tap
water
0.017
0.047
0.136
2.91
0.726
0.114
Ben etal .
(2020)
Iran (i) Azithromycin
(ii) Cefalexin
(iii) Ciprofloxacin
WWTP 0.563
0.184
0.657
Mirzaei etal .
(2019)
04. EUROPE Spain (i) Chlortetracycline
(ii) Clarithromycin
(iii) Ciprofloxacin
(iv) Enrofloxacin
(v) Lincomycin
(vi) Norfloxacin
(vii) Trimethoprim
(viii) Ofloxacin
Surface, waste
waters and
hospital effluent
0.059
0.01
0.74, 2.292,13.78
0.07,0.22
0.047,0.142
0.054,0.310
0.151,0.232
14.38
Díaz-Cruz
etal. (2008);
Rodriguez-
Mozaz etal.
(2015)
North
Portugual
(i) Ampicillin
(ii) Azythromycin
(iii) Clarithromycin
Urban
wastewater
0.552
0.184–0.358
0.433–0.474
Iakovides
etal. (2019)
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79A brief account of the antibiotics and antibiotic resistance genes in an aquatic environment
ARGs can persist in WWTPs even after treatment, as some of the ARG-carrying bacteria may be
resistant to the disinfectants and antibiotics used in the treatment process. In addition, some ARGs
can be transferred between bacteria through mechanisms such as horizontal gene transfer, which can
lead to the development and spread of antibiotic-resistant bacteria.
Researchers are exploring various strategies to reduce the occurrence of ARGs in WWTPs. For
example, advanced treatment technologies such as membrane filtration and ozonation have been
shown to be effective in removing ARGs from wastewater. Additionally, optimizing the treatment
process to promote the growth of bacteria that are not resistant to antibiotics may also help to reduce
the occurrence of ARGs in WWTPs. Overall, the detection of ARGs in WWTPs highlights the need
for improved wastewater management practices to minimize the environmental impact of antibiotics
and antibiotic-resistant bacteria. Continued monitoring and research will be necessary to better
understand the occurrence and fate of ARGs in WWTPs and to develop effective strategies for their
removal.
5.1.3 Global distribution of antibiotics as emerging pollutants
This study aims at the available literature for antibiotic utilization and their concentrations in various
aquatic bodies reported worldwide and presented in Table 5.2. The study formulated 16 studies among
all the continents of our globe, in which we reported some trends in the utilization of antibiotics in the
different corners of this small global world. Ciprofloxacin and fluoroquinolones had been reported as
the most persistent antibiotics in the studies.
Developing nations have a burden of microbial-induced mortality and, thereby, the utilization
of antibiotics. Agunbiade and Moodley (2016) reported a study in which nalidixic acid and
ciprofloxacin levels were detected in South African riverine waterways in the range of 25.2–29.5 µg/L
and 27.1 µg/L, respectively. These high concentrations are reported due to rivers receiving high
contamination from agricultural activities and lacking poor management of effluents. Another study
from Ghana, reported by Azanu et al. (2018), showed the highest concentrations in the order of
ciprofloxacin > erythromycin > sulfmethoxazole > ampicillin in the hospital wastewater effluents.
The highest concentration of sulfamethoxazole, with a concentration of 7.194 µg/L, had been reported
in W WTP effluent . Ampicill in was found to be t he least in the c oncentration of bot h hospital and W WTP
facility effluent. In Kenya, high concentrations of sulfamethoxazole (13.8 µg/L) and trimethoprim
(2.650 µg/L) have been reported due to the high disease prevalence, especially HIV/AIDS (Ngumba
etal., 2016). Similar trends were observed in Asian nations. As reported in Iraq, considerably high
levels are reported in the effluent from a drinking water treatment facility (Mahmood et al., 2019).
High concentrations were reported in China and India’s aquatic bodies, as reported in Tables 5.2 and
5.3, respectively.
The aquatic antibiotic levels in American countries ranged from 2 g/L or less, except for
sulfadimethoxine, which was detected at 15 g/L in Kansas, USA (Cha et al., 2006; Lindsey et al .,
2001). Ampicillin and oxacillin levels from WWTP wastewaters to the Cache la Poudre River in
northern Colorado have been documented at 86 and 95 g/L, respectively (Cha etal., 2006). Monensin
turned out to be the most often found molecule and was also discovered in larger quantities than
salinomycin and lascolid, in line with the various levels and types of livestock farming in the Del Plata
basin, Argentina (Alonso etal., 2019).
Based on the data available, European nations have reported a considerable amount of antibiotics
in various studies, whereas Spain reported the highest antibiotic consumption (Díaz-Cruz et al .,
2008 ). Healthcare facility effluents along the Ter River in Spain have been discovered to contain
substantial amounts of microchemical pollutants, including ofloxacin and ciprofloxacin, at quantities
above 13 g/L (Rodriguez-Mozaz et al., 2015), which may corroborate the high consumption in
Spain concerning other European nations. In France, clarithromycin had been reported as the
maximum concentration with a 2.33 µg/L value (Feitosa-Felizzola & Chiron, 2009). The authors
reported this due to the highly persistent nature of this chemical in the water bodies. Similarly,
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80 Detection and Treatment of Emerging Contaminants in Wastewater
ciprofloxacin reported 1.674 µg/L in influents and 0.626 µg/L in effluents at Varese Olona STP,
Italy, representing efficient reduction (Castiglioni etal., 2008). North Portugal had reported a trend
of ampicillin > clarithromycin > azithromycin > trimethoprim antibiotics in urban wastewater
(Iakovides etal., 2019).
Almost all of the concentration of the antibiotic has been reported in our farthest
destination, that is, the ice caps of Antarctica, where ciprofloxacin (in the range 0.37–1.86 µg/L)
and norfloxacin (0.58–1.23 µg/L) have been reported in the highest amount, followed by
metronidazole > clandinomycin > erythromycin > others. These traces can be assigned to significant
transport processes of the hydrological cycle, tourism, and international research stations in the area
(Hernández etal., 2019).
5.1.4 Studies for antibiotic distribution in Indian aquatic bodies
A brief literature review was conducted on the Indian subcontinent for the occurrence of these
persistent chemicals. Studies conducted by Philip et al. (2017) stated that 39% of antibiotic
contamination was found in the northern rivers Ganga and Yamuna. Both rivers are the lifeline of
Northern India, contaminated with pollutants from sources like effluents from industries, households,
and other agricultural activities carried out in the upper and lower stretches of the river. It is reported
that the sewage treatment plant (STP) effluent enters the river with reportedly high concentrations of
Table 5.3 Studies reported in different sectors with varied concentration of antibiotics from several states in India.
S.No. Type States Antibiotics Concentration
(µg/L)
References
River/Lake/T TP
1. Kshipra River Madhya
Pradesh
(i) Norfloxacin
(ii) Sulfamethoxazole
0.66
1.59
Diwan etal. (2018)
2. STP in South India Tamil Nadu
and Kerala
(i) Chloramphenicol
(ii) Trimethoprim
(iii) Sulfamethoxazole
(iv) Ofloxacin
<0.01
0.043–0.285
0.040–0.637
0.00–0.2469
Akiba etal. (2015)
3. Tamil Nadu
Shrimp farms
(i) Chloramphenicol
(ii) Sulfonamides
(iii) Erythromycin
0.085–0.123
44.12–72.65
1.32–2.45
Swapna etal. (2012)
4. Shrimp farm Karnataka (i) Chloramphenicol
(ii) Sulfonamides
(iii) Erythromycin
0– 0.0135
58.36– 69.65
53.69–56.98
Swapna etal. (2012)
5. Patancheru
Enviro Tech Ltd.
Treatment plant
undiluted effluent
(i) Ciprofloxacin
(ii) Enrofloxacin
(iii) Norfloxacin
(iv) Ofloxacin
(v) Lomefloxacin
4.4
14000
210
25
55
8.8
Fick etal. (2009)
6. Musi River (i) Ciprofloxacin
(ii) Oxofloxacin
(iii) Norfloxacin
5015
542.4
251
Gothwal and
Shashidhar (2017)
7. Yamuna R ive r Delhi (i) Ampicillin
(ii) Ciprofloxacin
(iii) Gatifloxacin
(iv) Sparfloxacin
(v) Cefuroxin
0.2–13.75
ND–1.4 4
ND–0.48
ND–2.09
ND–1.7
Monitoring etal.
(2014)
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81A brief account of the antibiotics and antibiotic resistance genes in an aquatic environment
fluoroquinolones ranging from Not in Detection Limit (NDL) to 2.09 µg/L (Monitoring etal., 2014).
Although values fluctuated due to temporal variations reported least in monsoonal climate followed
by summers and maximum in winters. This can be attributed to the hydraulic gradient of the riverine
system and also to more diseases in the winter seasons.
Arsson (2009) reported an unusually high amount of persistent antibiotics, particularly
trimethoprim (4.4 µg/L), ciprofloxacin (14,000 µg/L), enrofloxacin (210 µg/L), norfloxacin (25 µg/L),
ofloxacin (55 µg/L), and lomefloxacin (8.8 µg/L), found in the undiluted effluents from the Patancheru
Enviro Tech Ltd. (PETL) wastewater treatment plant in Hyderabad, which is the pharmaceutical
capital of India. Recent studies also reported high contamination in the Musi River, Hyderabad, as
PETL outlets drained it from 2009 onwards (Gothwal & Shashidhar, 2017). The situation is worst
reported in soil sediments, groundwater (well studies), effluent, and influent scenarios. Another study
from shrimp farms located in Hyderabad by Swapna etal. (2012) reported high levels of sulfonamide
in the range of 58.36–69.65 µg/L, erythromycin within 53.69–56.98 µg/L, and a mild concentration
of chloramphenicol ranged from 0 to 0.0135 µg/L. High concentrations can be attributed to animal
husbandry practices, poor implementation of water regulation policies, and negligence by government
authorities. Antibiotic medicines and their derivatives were discovered in wastewater and sludge from
three residential STPs in India’s southern states, conducted by Akiba e t al. (2015). Comparatively
temporally varied concentrations were reported in the Kshipra River. Norfloxacin was at 0.66 µg/L,
and ofloxacin was at 0.99 µg/L. According to reports, sulfamethoxazole was found at higher
concentrations in the fall and winter seasons (2.75 and 2.18 g/L, respectively) than in the summer
(1.39 and 0.04 g/L, respectively) (Diwan etal., 2018).
5.2 TRENDS IN CONSUMPTION OF ANTIBIOTIC POLLUTANTS
5.2.1 Antibiotic consumption trend at the global level
Universalizing the economies and the developed medical sector with better survival reports can be
accredited to the availability of these useful drugs to humanity. Estimates from 76 countries reveal
that the predicted global antibiotic use grew by 39% to 42.3 billion designated regular doses up to
15 years, that is, from 2000 and 2015 (Klein etal., 2018). Defined daily dose (DDD) is the estimated
daily sustaining dosage for a medication used in humans for its primary indication. By 2020, global
pharmaceutical spending would have increased by 29–32% from 2015 versus 35% in the previous five
years (Aitken, 2020) .
The predicted calculated global antibiotic consumption levels (such as in nations not listed in the
IQVIA inventory (IMS Health Quintiles)) significantly decreased between 2000 and 2015 in High-
Income Countries (HICs), ranging from 27.0 to 25.7 DDDs per 1000 residents per day, but increased
by approximately 77% in Low-Middle Income Countries (LMICs), from 8.6 to 13.9 DDDs per 1000
inhabitants per day (Klein et al., 2018). High-income nations used antibiotics more frequently per
person than low- and middle-income nations, including India, China, and Brazil, which had a
massive growth in antibiotic consumption. However, some fluctuating and considerate trends were
reported in the consumption of antibiotics. While the usage rates of the subsequent three categories of
antibiotics – cephalosporins (20% of all DDDs), quinolones (12% of all DDDs), and macrolides (12%
of all DDDs) – all increased globally between 2000 and 2015, the overall usage of antibiotics in HICs
reduced dramatically during that time. Usage of antibiotics surged 399%, 125%, and 119% in LMICs,
respectively, for cephalosporins, quinolones, and macrolides. These three medications’ antimicrobial
use rates in HICs declined by 18%, 1%, and 25%, respectively. Five countries with major emerging
economies, that is, Brazil, Russia, India, China, and South Africa (a group known as BRICS) (State &
The, 2015), recorded the highest increase in consumption of antibiotics in the first decade of the 21st
century (2000–2010). Between 2000 and 2010, these nations’ antibiotic usage increased by 68%, 19%,
66%, 37%, and 219%, respectively. Although these BRICS countries accounted for nearly 75% of world
consumption growth, per capita spending in these nations remained lower than in the developed USA
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82 Detection and Treatment of Emerging Contaminants in Wastewater
(CDDEP, 2015; State & The,2015). Despite this, as their populations grow, it is anticipated that in
BRICS nations, usage will double by 2030, presuming no legislative changes.
5.2.2 Antibiotic consumption trend in India
With nearly 1.3 billion inhabitants, India is the fastest-growing second-most populated nation on the
planet and has half a billion animals, accounting for 20% of the world’s total livestock population.
Being an agrarian and developing nation, the use of antibiotics has been on a tremendous rise to
meet the requirement of eatables (dairy products) and healthcare facilities for such a huge population
expansion, which is estimated to rise by two-thirds between 2010 and 2030 (Laxminarayan &
Chaudhury, 2016) . India also has the world’s largest cattle and poultry population with a sizable
aquaculture industry, which consumes vast quantities of antibiotics to maximize yield. The use
of prophylactic antibiotics in animal husbandry and aquaculture is increasing antibiotic-resistant
pathogens, which remains a grave concern (Ghosh & Mandal, 2010) . Technological innovation,
formal investigation, trained employees, relatively low cost, and a paucity of patent protection make
the Indian market an appealing alternative for global multinational businesses looking to outsource
their medication manufacturing.
In terms of pharmaceutical output and consumption, India is ranked third and thirteenth in the
world, respectively. Rapid urbanization has been reported in India during the last three decades,
which synergistically degrades and upgrades the quality of life. Bacterial infections, enteric fever,
diarrhea, cholera, and acute respiratory infections are the undemanded repercussions of the teeming
ambient of urban land. One of the main contributing factors to the inappropriate and unregulated use
of antibiotics in India is the purchase of antibiotics without a prescription from pharmacies.
Antibiotic usage in India increased by 103% (3.2–6.5 billion specified daily doses) in the previous
15 years (2000–2015) (Klein etal., 2018). In LMICs, India saw the highest rise in antibiotic use (65%
between 2000 and 2015) and continued economic development (a 10% annual increase in Gross
Domestic Product [GDP] during the 2000s. India’s per capita usage of antibiotics (10.7 units per
capita) was less than that of numerous other countries during this moment (e.g., 22 units per capita
in the USA) (‘Scoping Report on Antimicrobial Resistance in India’, 2017). In 2010, the utilization of
antimicrobial compounds in food animals was projected to be ∼63,000 (1560) units; India holds 3%
of the global demand and is the fourth largest exporter, after China (23%), the USA (13%), and Brazil
(9%). Antimicrobial usage in India’s food animal industry is predicted to quadruple by 2030.
However, in India, there were some reported trends in this particular class of antibiotics from
2000 to 2015. After quinolones (34%), cephalosporins (32%), macrolides (14%), and tetracyclines (6%),
penicillins were the third most regularly given antibiotics in 28% of cases (Kotwani and Holloway,
2011 ). In 2012, India exceeded expectations as the world’s largest user of oxazolidinone antibiotics.
5.3 ECOLOGICAL RISK POSED BY ANTIBIOTICS
Previous sections described the occurrence and possible sources of antibiotic channeling into
our ecosystem components, mainly water and soil, as shown in Figure 5.2. Industrial activities,
household waste effluent, and agricultural activities are the sources of the most intensive utilization
of antibiotics. These sources contaminate the surface water bodies through improper disposal and
runoff, physio-chemically trapped traces into soil sediments, and en-route into the groundwater
table via leaching. Subsequently, these contaminated sources are used for irrigation purposes and
bioaccumulate in the edible crop plants, ultimately reaching our plates at a much higher level. The
vicious cycle of biotransformation, bioaccumulation, and biogeochemical cycling processes tends
to aggravate the issue of increased risk. Antibiotics released without sufficient treatment have led
to substantial levels of antibiotic remnants in the aquatic system, as mentioned in earlier sections.
Many cases of antibiotic resistance have been reported in the last two decades, which has given
rise to serious health concerns for livestock and the human population. The widespread antibiotic
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83A brief account of the antibiotics and antibiotic resistance genes in an aquatic environment
tetracycline, which is routinely used to cure both humans and animals, has been discovered to cause
horizontal translocation of resistance genes in Escherichia coli at low doses in the microgram per
liter range (Grenni et al., 2018 ). Low concentrations mean non-lethal or sub-inhibitory ones tend to
act in different ways, such as in selecting resistances, by generating genetic and phenotypic alterations
to promote adaptive evolution, and as signaling molecules to produce other physiological functions
(Müller etal., 2002).
Although there was less research on antibiotic risk evaluation in India’s aquatic systems,
numerous studies have found a prevalence of antibiotic resistance in areas where antibiotic
pollution is a problem. The persistent nature of antibiotics tends to be antibiotic resistance, ARGs,
and antimicrobial resistance (AMR), which developed due to rampant and unregulated usage of
antibiotics. Bacterial resistance is a significant adjustment or systemic response of microbes to
substances that attempt to stop them from growing, and it is developed through many processes, as
previously stated. According to a recent analysis, drug-resistant diseases kill 700,000 people every
year, with 10 million people dying annually by 2050 (Proia et al., 2018 ). Antibiotic resistance is
likely to impede the battle against HIV and malaria, with 490,000 people developing multi-drug-
resistant TB worldwide in 2016. E. coli has a high resilience rate to fluoroquinolone therapies (one
of the most regularly used drugs for treating urinary incontinence). In at least 10 nations, treatment
failure with the final resort of gonorrhea medication (third-generation cephalosporin antibiotics)
has been proven. As of July 2016, five countries in the Greater Mekong subregion had demonstrated
resistance to the first-line therapy for Plasmodium falciparum malaria (artemisinin-based combo
regimens).
Being the antibiotic manufacturer capital of the world, India suffers from this catastrophe of
drug resistance. India has one of the highest proportions of bacterial illnesses in the world. In India,
approximately 410,000 children aged five and under perish from pneumonia each year, accounting for
about a quarter of all child mortality. The crude death rate from contagious diseases in India is now
417 per 100,000 people (‘Scoping Report on Antimicrobial Resistance in India’, 2017).
Antibiotic residues can alter ecological integrity in general. Antibiotics, which are substances
that may damage or limit the development of microorganisms, are likely to upset the environment’s
microbiome equilibrium. The microbiological community of aquatic bodies plays a significant role
in channeling their ecological health. Due to the influence of persistent antibiotics, agricultural
fields watered with wastewater and polluted with antibiotic residues may deplete the key microbial
group for nitrification. On the other hand, antibiotic residues in wastewater can disturb the activity
of microorganisms engaged in the disposal of both residential (septic tanks) and industrial effluents
(W W TPs).
Antibiotic cocktails synergistically adversely and significantly affect the food web of the aquatic
body, rather than the presence of singlets (Danner et al ., 2019). Chen et a l. (2018) reported the
synergistic actions of the combination of tetracycline and enrofloxacin. The authors reported the
increased risk of biochemical transformation of reaction products after the interaction of two or
more antibiotics instead of their existence, which may or may not be harmful to humans (Kumari &
Kumar, 2020).
5.4 ASSESSMENT AND REMEDIATION METHODOLOGIES
Antibiotics are non-biodegradable, and several of them have been found to linger in the soil.
Various studies have been reported by Grenni etal. (2018) on the newly introduced concept of the
biodegradability of antibiotics by the available microbial community. The other noted effects of
antibiotics can be seen in an altered pattern of ecological functions like methanogenesis, sulfate
reduction, nutrient cycling, nitrogen transformation, and the rate of humus formation (Grenni etal.,
2018). Apart from that, the basal metabolic rate of an aquatic body also fluctuates due to changes in
physio-chemical and biological parameters.
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84 Detection and Treatment of Emerging Contaminants in Wastewater
Although the persistence of antibiotics in the effluents of different residential, commercial, and
other institutional sectors creates a nuisance for their proper disposal and treatment for sustainable
medical management, fewer available technologies are there to solve this challenge. Although
conventional treatment technologies are not designed for emerging contaminants, conventional
treatment processes such as coagulation, flocculation, and sedimentation can be partially used for the
remediation of antibiotics in the aquatic system. Various studies support the fact that the combination
of different advanced treatment processes efficiently removes them to a satisfactory level. Hence, it
emphasizes the necessity of a synergistic and integrative approach to treating wastewater containing
antibiotics.
Each methodology has its own set of dimensions, both positive (effective removal, low cost)
and negative (cost factor, high maintenance). There is a practical need for an integrative approach
to applying the treatment methodologies for better management and application processes. A
conventional (activated sludge) and cutting-edge (membrane filtration/osmosis) effluent treatment
facility in Brisbane, Australia, which excludes antibiotics, showed that both treatment processes
substantially lowered antibiotic quantities, with an average removal efficiency of 92% from the liquid
stage (Wat kinson etal., 2007). Antibiotics had been discovered in both effluents in the low to mid-
nanogram per liter range. But the concentration findings in the advanced methodology’s treated
effluent were lower than the conventional ones.
5.4.1 Conventional treatment processes
The goal of conventional water treatment is to guarantee that water is safe to drink by removing
physiological, tangible, and microbiological pollutants such as heavy metals, suspended solids, and
spoilage microorganisms. These water-treatment methods are usually not designed to extract trace
contaminants. Although some researchers have confirmed that traditional WWTPs may remove Abs,
they must use processes including coagulation, precipitation, sand filtering, and clarifying.
5.4.1.1 Activated sludge process (ASP)
In municipal WWTPs, activated sludge is mingled with wastewater and microbes to remove
micronutrients that oxidize carbon-containing biological matter and other compounds throughout the
treatment process. High removal efficiency varied from 30% to 70% reported, with a very unusually
long retention time reported for the removal of sulfonamides, macrolides, and trimethoprim by the
activated sludge process (Göbel etal., 2005).
5.4.1.2 Membrane biological reactor (MBR)
MBR involves a series of actions required to achieve higher effic acy. Ab elimination through wastew ater
treatment mainly incorporates microbial degradation, affinity to sludge, photocatalytic degradation,
and evaporation. When combined with ASP, this approach produces less sediment, lower suspended
particles, and higher germ elimination, making it ideal for domestic wastewater. Longer retention
times allow denitrification, increased bacterial nitrification activity, and improved micropollutant
elimination.
5.4.2 Advanced emerging treatment techniques
Antibiotic pollution in water is a significant environmental and public health concern. The emergence
of antibiotic-resistant bacteria due to the presence of antibiotics in water has led to a growing need
for effective treatment methods. Emerging techniques such as advanced oxidation processes (AOPs),
adsorption, and membrane filtration have shown promise in removing antibiotics from water. AOPs
involve the generation of highly reactive oxidizing species that can degrade antibiotics. Adsorption
involves the use of materials with a high surface area and adsorption capacity to remove antibiotics
from water. Membrane filtration uses membranes with small pores to physically remove antibiotics
from water. The following section discusses these emerging techniques, which have the potential to
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85A brief account of the antibiotics and antibiotic resistance genes in an aquatic environment
improve the quality of water and reduce the risk of antibiotic-resistant bacteria, but further research is
needed to optimize their effectiveness and feasibility for large-scale implementation.
The use of a composite of modern methods of treatment such as hydroxyl radicals, catalyst
supports, photovoltaic, or ultraviolet (UV) light to eliminate antibiotics from wastewater has lately
received interest. AOPs generate the hydroxyl radical (•OH), which is a potent antioxidant or oxidative
radical that reacts with molecules (Anjali & Shanthakumar, 2019). The desired substances can then
be processed and oxidized into CO2, H2O, and inorganic materials.
Ultraviolet Photolysis of Hydrogen Peroxide (UV/H2O2), Photo-Fenton Process (UV/H2O2/Fe2+),
and ozonation methods have a high clearance rate (Biancullo etal., 2019). Except for metronidazole
(92%) and ciprofloxacin (100%), antibiotics are destroyed up to 100% under various experimental
settings using UV/H2O2 and ozonation approaches (93%). In antibiotics, UV/H2O2/Fe2+ reveals a
disintegration rate of up to 100% (Anjali & Shanthakumar, 2019).
5.4.2.1 Ozonation
By inducing oxidative stress, ozonation is used as a first-line solution to improve the processability
of contaminants (Blaney, 2014). Ozonation can utilize minimal energy and recover up to 99% of the
water without producing trash. Antibiotics are often removed from water and effluent via ozonation
and certain other oxidizing techniques. Iakovides et al. (2019) had undertaken research using
ozonation to eliminate antibiotics from unpasteurized milk for the first time (amoxicillin, doxycycline,
ciprofloxacin, and sulfadiazine).
5.4.2.2 UV irradiation
UV ir radiation is used for decont amination and is com monly employed in WWT Ps as part of t he tertiary
treatment. UV therapy breaks down chemical bonds in contaminants using UV light, a process known
as ‘photocatalytic degradation.’ On contrary, intense UV photocatalysis does not work efficiently. To
improve the efficacy of the treatment, a variety of UV lamps, moderate or reduced mercur y vapor lamps
generating Ultraviolet C (UV-C) light, and oxidants or catalysts (e.g., H2O2, Fe2+/3+, TiO2) were added.
UV irradiation coupled with advanced peroxidation (including UV/chlorine, UV/H2O2,UV/O3, and
H2O2/Fe2+/UV (photo-Fenton)) may accelerate Antibiotic Resistant Bacteria (ARB) and Antibiotic
Resistance Gene (ARG) elimination in potable water. UV irradiation is used for decontamination, and
UV light-emitting diodes have recently attracted a lot of interest in their development, particularly for
industrial wastewater treatment, due to their eco-friendliness (by substituting mercury) and sustained
period (Biancullo etal., 2019).
5.4.2.3 Adsorption-based removal
The aggregation of substances from a gaseous stage to the sorbent surface, which might be physical or
chemical, is referred to as adsorption (Mahmoud et al ., 2020). Four stages are involved in the removal
of impur ities: (i) mass solute mobilit y, (ii) ad sorbate layer propagation, (ii i) adsorbate di ffusion through
porosity, and (iv) adsorption – interplay among adsorbate and permeable morphology. The primary
mechanisms identified for carbon-based nanomaterials include hydrogen bonding, separation into
uncarbonized components, cavity loading, electrostatic effect (ionic attractions), hydrodynamic
impact (water-insoluble action), and a few more processes like surface deposition and so on. The
parameters of the adsorbent, such as effective surface area, permeability (macro or microporosity),
channel width, and functional groups, are all intrinsically linked to adsorption effectiveness.
The effectiveness of various adsorbents in eliminating antibiotics from wastewater was assessed by
looking at the adsorption coefficient values. Different sorbents for sulfamethoxazole followed a similar
trend: charcoal Biochar (BC) > Multiwalled Carbon NanoTubes (MWCNT) > graphite = silicate
minerals. T he adsorptive materia ls for tetracycline continued the pat tern: activated carbon (AC) = humic
material = clay particles = Single Walled Carbon Nanotubes (SWCNT) > graphite > MWCNT (Ahmed
etal., 2015).
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86 Detection and Treatment of Emerging Contaminants in Wastewater
5.4.2.3.1 Activated carbon (AC)
It is one of the most commonly cited adsorbents for removing antibiotics. Recent research on using
air conditioners (ACs) for antibiotic elimination has found that ACs or enhanced ACs may efficiently
separate a wide range of antibiotics from wastewater, ranging from 74% to 100%. After 24 hours of
adsorption, the most significant chemical oxygen demand (COD) removal of more than 90% was
achieved at a pH of 5, the operating temperature of 20°C, 0.15 g of activated carbon, and a 100 ppm
baseline tetracycline dosage (Profile, 2019).
5.4.2.3.2 Carbon nanotubes (CNTs)
CNTs are made up of tubular, stacked graphite sheets with a huge surface area and a significant
van der Waals index. Because sp2-hybridized carbon atoms are present, the benzenoid chains in
graphene-layered sheets have a strong dipole moment. The interaction between CNTs and aromatic
contaminants typically involves adsorption, where the hydrophobic nature of CNTs allows them
to adsorb or capture the hydrophobic aromatic compounds. This process often relies on van der
Waals forces or π-π stacking interactions between the carbon nanotubes and the aromatic rings of the
contaminants. Lincomycin and sulfamethoxazole (sulfonamides) were reported to be removed from
aqueous solutions by SWCNT and MWCNT in current antibiotic remediation experiments.
5.4.2.3.3 Ionic exchange resins
Ion exchange is a technique for transferring excited ions on a solid sorbent for metallic ions or negative
ions in a liquid solution while retaining electro-neutrality throughout the process. Overall, it has
been demonstrated that ion exchange resin hybrids are up to 90% efficient in eliminating antibiotics
from wastewater and drinking water. Accordingly, tetracyclines and sulfonamides had adsorption
reduction effectiveness of 80% and 90% on an ion exchanger.
5.5 REGULATIONS BY GLOBAL AUTHORITIES FOR ANTIBIOTICS UTILIZATION
With the introduction of new sophisticated and analytical tools and techniques, the detection of antibiotics
in trace amounts, their eco-toxicological studies, and hence the formulation of regulatory measures, became
possible recently. Governments across the globe are revising the standards for water quality parameters, and
it has been shown by the steps procured by the Indian government by amending the Environment Protection
Act (EPA), 1986, in January 2020. The Central Government amended the EPA of 1986 to formulate the
standard for traces of antibiotic presence in STP/ETP effluents from bulk drug and manufacturer industries.
The values suggested and disposed of nowadays are nowhere compared because of the unregulated and
inappropriate washing of antibiotics in water bodies. This act will put a hold on and check measures on
regulating the quality of effluents entering Indian rivers and other aquatic bodies (Authority, 2013).
The legal framework governing fish farming procedures differs from that of the poultry and dairy
industries. Antibiotics and numerous pharmacologically active compounds have been outlawed in
fisheries by the Food Safety and Standards Authority of India (FSSAI). On the other hand, there are no
regulations in the chicken business, and many commercially available blended meals include antibiotics.
Since March 2014, the Drugs and Cosmetic Rules, 1945 has included a distinct Schedule H-1 to control
the sale of antimicrobials nationwide. The schedule covers about 24 antimicrobials, including third
and fourth-generation cephalosporins and carbapenems. Antimicrobials cannot be dispensed without
a legitimate medical recommendation, and the medicine container must have the following phrase with
a red border: ‘Schedule H1 Drug–Warning: Taking the drug without professional counsel is harmful;
not to be distributed by retail without a licensed medical practitioner’s authorization.’ The pharmacist
must keep a separate register with information on the physician, the patient, and the medicine sold.
As part of the study, 30 possible policy options disseminated throughout the pollutant life cycle’s
10 primary probable action regions have been identified to inform the development of the European
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87A brief account of the antibiotics and antibiotic resistance genes in an aquatic environment
Union’s (EU) strategic approach. The objectives of these options are to (i) obtain a better knowledge
of the issue and (ii) establish circular economy-compliant, more efficient, and sustainable strategies
for manufacturing, utilization, and dumping.
The Food & Agricultural Organization (FAO) Action Plan on AMR contains five strategic priorities that
are in accordance with the international action plan having common goals: (i) enhance consciousness of
drug resistance; (ii) develop stronger expertise through vigilance and investigations; (iii) reduce the incidence
of infection; (iv) improve the use of antimicrobial agents in the wellness, animal, and food sectors; and (v)
establish the monetary justification for sustainable investing that caters to the needs of all nations, and
boost investment in new medicines, diagnostics, and vaccines. The actions have been started by the various
administrative units across the globe, but a comprehensive, integrative, and realistic strategy to combat
the problem of antibiotic resistance is the need of the hour. Strict punitive actions and regulations must be
directed at pharmaceutical companies to avoid more severe and lethal repercussions that are on their way.
5.6 CURRENT ADVANCES AND FUTURE OUTLOOK
Antibiotic resistance is a major public health concern worldwide. It is well known that the overuse
and misuse of antibiotics in human and animal health care can lead to the emergence and spread of
antibiotic-resistant bacteria. However, research has shown that the presence of antibiotics and ARGs
in the aquatic environment can also contribute to the development and spread of antibiotic-resistant
bacteria. Recent research has focused on understanding the fate and behavior of antibiotics and ARGs
in the aquatic environment. Studies have shown that antibiotics can persist in the environment for
long periods of time, even after they have been discontinued. Antibiotics can enter aquatic systems
through a variety of sources, including wastewater discharge from hospitals, farms, and households.
Current research in this area has focused on several key areas:
(a) Identifying the sources and pathways of antibiotics and ARGs in aquatic environments: Studies
have shown that the release of antibiotics and ARGs into aquatic environments can occur via
a variety of pathways, including wastewater discharges, agricultural runoff, and the use of
antibiotics in aquaculture.
(b) Developing methods for detecting and quantifying antibiotics and ARGs in aquatic
environments: There is ongoing research into the development of more sensitive and accurate
methods for detecting antibiotics and ARGs in water and sediment samples, such as Polymeric
Chain Reaction (PCR) -based assays and metagenomics.
(c) Understanding the fate and behavior of antibiotics and ARGs in aquatic environments:
Researchers are investigating the mechanisms by which antibiotics and ARGs are transported,
transformed, and degraded in aquatic environments and how their persistence can be
influenced by factors such as water chemistry, sediment characteristics, and microbial activity.
(d) Assessing the ecological and human health impacts of antibiotics and ARGs in aquatic
environments: Studies have shown that exposure to antibiotics and ARGs can have negative
effects on aquatic organisms, such as reducing their survival, growth, and reproduction. There
are also concerns about the potential for antibiotic resistance to spread to human pathogens
through the aquatic environment.
Researchers are exploring various strategies to mitigate the impact of antibiotics and ARGs in
the aquatic environment. For example, W WTPs can use advanced treatment technologies to remove
antibiotics and ARGs from wastewater before it is discharged into waterways. Additionally, some
researchers are exploring the use of phages, which are viruses that can infect and kill bacteria, as a
potential treatment for antibiotic-resistant bacteria in the aquatic environment. Looking to the future,
it is likely that the issue of antibiotics and ARGs in the aquatic environment will continue to be
an important area of research. Continued monitoring of water quality and the development of new
treatment technologies will be necessary to reduce the spread of antibiotic-resistant bacteria and
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88 Detection and Treatment of Emerging Contaminants in Wastewater
protect public health. Additionally, improved regulations and guidelines for the use and disposal of
antibiotics can help minimize the environmental impact of these drugs. Future research in this area
is likely to focus on several key areas:
(a) Developing s trateg ies for reducing t he release of a ntibiotics a nd ARGs into aqu atic envir onments:
This could involve improved wastewater treatment technologies, more sustainable agricultural
practices, and a reduced use of antibiotics in aquaculture.
(b) Developing new approaches for removing antibiotics and ARGs from aquatic environments:
Researchers are investigating the potential of various technologies, such as bioremediation,
nanotechnology, and adsorption, for removing antibiotics and ARGs from water and
sediment.
(c) Investigating the link between antibiotic use in humans and animals and the presence of
antibiotics and ARGs in aquatic environments: Studies are needed to better understand the
relationship between human and animal antibiotic use and the occurrence of antibiotics and
ARGs in aquatic environments, as well as the potential for exposure and transmission of
antibiotic resistance through the aquatic environment.
(d) Assessing the long-term effects of antibiotics and ARGs on aquatic ecosystems: There is a
need for more long-term studies to understand the potential ecological impacts of exposure to
antibiotics and ARGs over time and to identify the most vulnerable aquatic ecosystems and
organisms.
5.7 CONCLUSION
In conclusion, antibiotics have transformed modern medicine and enhanced the quality of life for
mil lions of people. However, the pr esence of antibiot ics and ARGs i n aquatic env ironments i s a mounting
concern that entails urgent consideration. The aquatic environment, including both freshwater and
marine ecosystems, has been documented as a reservoir of ARGs and antibiotic-resistant bacteria.
The discharge of antibiotics and their residues into the aquatic environment from various sources,
including agricultural and medical activities, is believed to contribute to the dissemination and
persistence of ARGs. These compounds can have harmful effects on aquatic organisms and contribute
to the development of antibiotic-resistant bacteria, which pose a significant threat to human health.
Thus, understanding the dynamics of antibiotic resistance in the aquatic environment is crucial to
mitigating the spread of ARGs and developing effective strategies to combat antibiotic resistance.
This can be achieved through the development and implementation of regulations, the promotion of
responsible use of antibiotics, and the adoption of appropriate treatment technologies for wastewater.
Further research is also needed to understand the extent and distribution of antibiotics and ARGs
in different aquatic environments, as well as their impacts on ecosystem health and human well-
being. By taking concerted actions, we can protect our precious aquatic resources and prevent the
emergence and spread of antibiotic-resistant bacteria.
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© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0093
Paramjeet Dhull1, Neha Saini1, Mohd Aamir2, Shama Parveen3 and Samina Husain4*
1Department of Environmental Science & Engineering, Guru Jambheshwar University of Science & Technology, Hisar 125001,
Haryana, India
2Division of Plant Pathology, ICAR-Indian Council of Agricultural Research, Pusa, New Delhi 110012, India
3Department of Physics, DPG Degree College, Gurugram, India
4Centre for Nanoscience and Nanotechnology, Jamia Millia Islamia, New Delhi 110025, India
*Corresponding author: shusain3@jmi.ac.in
ABSTRACT
Freshwater accessibility has grown to be a serious global challenge. The naturally occurring freshwater
reserves are contaminated by the increased demographic, industrialization, and climatic changes. The health,
environment, economy, and daily life are all extremely harmed by water pollution. Emergent pollutants including
microplastics, antibiotics, hormones, unregulated medicines, nano-based materials, endocrine disruptors,
pesticides, and so on are detrimental to human health and the environment. The development of wastewater
treatment methods that are quick, feasible, low-cost, efficient, and sustainable is a problem posed by the
emergence of new pollutants in the water. The shor tcomings of current traditional treatment methods can
be reduced with nanotechnology’s intervention as it can remediate the contaminants commonly found in
traces within complex organic mineral compounds. Based on the types of pollutants and required level of
treatment efficiency, several nanomaterials such as carbon nanotubes, nanocomposites, nano-sorbents,
graphene, nanomembranes, nanofibers, and nano-catalysts and so on are employed for wastewater treatment.
Nanomaterials have unique physcio-chemical properties like shape, size and structure, surface morphology,
crystallinity, and so on. These special qualities make them ideal substitutes for wastewater cleanup, purification,
and contamination detection using pollutant-specific nanosensors and detectors. This chapter covers the type
of nanomaterials and nanotechnologies useful in wastewater treatment to remediate emerging pollutants of
concern. It also discusses the toxicity associated with nanotechnology and its environmental concern. Further
the recent trends of large-scale clean-up of wastewater using nanotechnology and the challenges and future
perspective associated with it are discussed.
Keywords: emerging contaminants (ECs), nanomaterials, wastewater treatment, nanoparticles, green synthesis,
eco-toxicity
Chapter 6
Function of nanomaterials in the
treatment of emerging pollutants
inwastewater
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94 Detection and Treatment of Emerging Contaminants in Wastewater
6.1 INTRODUCTION
As we all know, the availability of water in a pure state is becoming very crucial for the survival of
human beings and other life forms (Kurniawan e t al., 2023). It is regarded as a universal solvent
because of its special properties such as solubility. Clean and unpolluted water access to everyone
has become a major challenge for the whole world (Sufiani etal., 2023). Further, the ever-increasing
world population and industrialization demand more and more clean water for various activities
like drinking, agriculture, industrial activities, transportation, and many more. As reported, the
world’s water requirement has doubled from a few decades ago and it has become a global issue and a
major challenge for the life in 21st century (Hodges etal., 2018). Due to reasons like the dumping of
industrial wastes, sewage treatment, marine dumping issues, dumping of radioactive waste materials,
agricultural run-offs directly into water bodies, and so on lead to the introduction of emerging
contaminants (ECs) into the water bodies. These excessive amounts of pollutants and ECs render
them unsuitable for usage (Yaqoob et al., 2020). The organic pollutants, also known as ECs, have
drawn the attention of the public and raised concerns since they not only worsen the quality of
water but also present a serious risk to already-installed water treatment systems and have recently
been identified as a major hazardous pollutant (Rathi et al ., 2021). These are natural or artificial
compounds/substances that are mainly unregulated. Indeed, these are not necessarily of new use
but are newly identified and the knowledge about their presence, sources, fate, and effects are not
completely known. The long list includes pharmaceutical compounds like analgesics, antidepressants,
hormones, antibiotics, lipid regulators, anti-inflammatory drugs, personal care products like fats,
fragrances, sunscreens, detergents, oils, disinfectants, and insect repellants (Morin-Crini etal., 2022);
pesticides; fertilizers; sweeteners; polycyclic aromatic hydrocarbons (PAHs); dioxins; surfactants,
and other chemicals, often not effectively removed by conventional wastewater treatment processes
(Ahmed etal., 2021; Rout etal., 2021). These are often released into water bodies from point sources
of industries, domestic effluents, agriculture, hospitals, aquaculture, and so on. They are introduced
into groundwater through infiltration, leakage, leaching from landfills, leakage from septic tanks, or
failure with sewage systems (Parida et al., 2021). Due to the benefits provided by these products in
the daily lifestyle, these are utilized and released continuously into the environment, even at very low
concentrations (ng/L to µg/L). As a result, they can accumulate in water bodies, leading to potential
ecological and human health risks like carcinogenicity and tissue degradation which are extremely
hazardous, the development of antibiotic-resistant bacteria, and so on (Karpińska & Kotowska, 2021).
Table 6.1 discusses the present emerging contaminant (EC) types, their sources, and the consequences
which they pose to human and environmental health.
Currently, EC treatment technologies applied in wastewater treatment plants (WWTPs) are of
two kinds that is, conventional treatment and advanced treatment techniques including physical,
mechanical, chemical, and biological methods (Wen et al., 2021). These treatment technologies are
based on the fate of the water to be used for industr y, agriculture, drin king, and domestic purpose. Most
commonly used methods include filtration, ozonation, biochemical processes, chemical disinfection,
dilut ion, photolysis, sorpt ion, biodegrad ation, deconta mination t reatment, s edimentat ion, flocculat ion,
volatilization, and so on (Rout et a l., 2021). Further, advanced processes like adsorption-oriented
processes and advanced oxidation processes including biosorbents, biological-based technologies,
activated carbon, and biochar have also occupied the focus of WW TPs research for the exclusion of ECs
(Cheng etal., 2021; Morin-Crini etal., 2022). Regardless, existing WWTPs treatment technologies are
not able to completely eliminate emerging contaminants in the wastewater because of their complex
and non-biodegradability structure, polarity, and high-water solubility (Alvarino etal., 2018). These
treatment technologies pose several limitations like high operating and maintenance costs, lower
efficiency, selective decontamination, large-scale applications, high energy requirement, production
of harmful by-products, and so on (Mirzaei etal., 2017). These drawbacks led researchers to explore
improved and innovative technologies which are sustainable and eco-friendly.
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95Function of nanomaterials in the treatment of emerging pollutants inwastewater
Table 6.1 Types of emerging contaminants (ECs) and their consequences on human health and environment.
EC Types Representative ECs Major Sources Adverse Effects References
Pharmaceutically
active compounds
(Ph ACs)
Diazepam, Testosterone,
Diclofenac, Clorfibric acid,
Ciprofloxacin, Metoprolol,
Carbamazepine,
Hospital effluent,
pharmaceutical industry
effluent, domestic
wastewater, livestock, and
aquaculture farms effluent
Induces antibiotic resistance in
microbes, affects the structure
of the microbial community, and
reduces the population of nematodes,
bacteria, algae, and so on.
Ahmed etal.
(2021), K han etal.
(2021), Rout etal.
(2021), Morin-
Crini etal. (2022)
Personal care
products (PCPs) N′-diethyltoluamide (DEET),
galaxolide, 4-benzophenone,
N, musk xylene, musk ketone
Surface water, WWTP
effluent, and landfill
leachate
Enhances toxicity in the aquatic
environment, causes oxidation stress
to goldfish, is carcinogenic to rodents,
and potentially causes damage to the
human nervous system
Perfluorinated
alkylated substances
(PFA Ss)
Perfluorooctanoic
acid (PFOA) and
perfluorooctanesulfonate
(PFOS)
Surface water,
wastewater, groundwater,
and sediments
Kidney cancer, liver damage, thyroid
disease, induces resistance to
vaccines, and developmental effects
on the unborn child.
Endocrine-disrupting
chemicals (EDCs)
Bisphenol A (BPA),
phthalates, dioctyl phthalate
(DOP), xenoestrogen, and
bisphenol,
Secondary sludge,
drinking water, soil,
surface water, and
sediments
Interfere with the endocrine system,
estrogenic effects in rats, feminizing
side effects in men, birth defects, and
developmental delays.
Regulated compounds
(RCs)
Phenanthrene, anthracene,
pyrene and chlorpyrifos
Surface water, soils,
agricultural runoffs,
sediment, effluent from
sewage treatment plants,
Cardiovascular diseases, carcinogenic
effects, poor fetal development
Industrial chemicals Tris (1-chloro−2-propyl)
phosphate (TCPP),
polybrominated diphenyl
ethers (PBDEs) and dimethyl
adipate (DMAD)
Industrial effluent and
domestic wastewater
Affect hormonal activity, interfere
with brain and nervous system,
reproduction, and fertility
Pesticides Metaldehyde, butachlor, and
epoxiconazole
Aquaculture effluent,
agricultural runoff, and
surface water
Carcinogenic effect, cardiovascular
diseases, toxic to aquatic organisms
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96 Detection and Treatment of Emerging Contaminants in Wastewater
In this scenario, it is possible to view nanomaterials and nanotechnologies as a feasible and
successful way to get beyond the drawbacks of conventional and innovative wastewater treatment
approaches (Karthigadevi et al., 2021). These have emerged as a low-expense, more efficient option
for the removal of ECs from wastewater. Because of their properties such as organophilic nature, sieve
diameter, strong solution mobility, aspect ratio, sensitivity, selectivity, catalytic potential, tunable
hydrophobicity, large surface area, absorptivity, antimicrobial properties, porosity, strong mechanical
properties, recyclability, chemical stability, mobility, and many more makes them the better option to
remove/treat emerging contaminants from wastewater (Wu et al., 2019; Yaqoob & Ibrahim, 2019).
Recently, there have been improvements in the research and development of nanomaterials such as
nanomembranes, nanomotors, nanofiltration membranes, nanosorbents, engineered nanomaterials
like nanocomposites, and so on which have shown effective removal of ECs from wastewater and have
opened new opportunities to adapt towards both selectivity and capacity of particular ECs (Ollier
etal., 2020). Fang etal. (2017) found effective removal for Pb2+, Cd2+, and Cu2+ with an adsorption
capacity of 20.23 mg Pb/g, 17.01 mg Cd/g, and 10.42 mg Cu/g, respectively, through PDA nanoparticle
adhering on the walls of finger-like pores (PES/PDA-R). Adsorption capabilities were found to be
1.69, 2.25, and 1.91 times more, respectively, than in conventional PDA-decorated membranes (PES/
PDA-F membranes). Other studies have also reported the efficiency of nanofiltration membrane-
based nanomaterials for the elimination of ECs emerged from personal care goods, pesticides, and
pharmaceuticals (Kollarahithlu & Balakrishnan, 2021).
This chapter provides a thorough explanation of how nanomaterials work for controlling emerging
contaminants (ECs) in wastewater. It will discuss several kinds of nanomaterials, such as carbon-
based nanomaterials, metal, and metal oxide nanoparticles, and hybrid nanocomposites, as well
as their applications in the elimination and degradation of emerging contaminants. It will cover
the latest advancements in the field, including the synthesis, characterization, mechanisms, and
factors influencing their performance and application for the degradation and removal of emerging
pollutants. It will provide insights into the latest advances and new developments in the application
of nanomaterials to the pressing problem of emerging contaminants in wastewater and offer potential
solutions for sustainable water management in the future. The chapter will further highlight the
challenges and future prospects of their application in this field including their potential impacts on
the environment and human health. It will provide insights into the current state of the field, and
identify knowledge gaps in this rapidly evolving area of environmental science and engineering.
6.2 CLASSIFICATION OF NANOMATERIALS (NMS)
Contaminated water adversely affects all ecosystems, predominantly aquatic and terrestrial
ecosystems, and human health. The availability of pure water is a global challenge for the whole world
in the 21st century because, without water, all living beings’ existence is impossible. To overcome
this severe concern, several techniques were used in ancient times to purify water, such as micro-
ultrafiltration, reverse osmosis, sedimentation, and precipitation (Anjum etal., 2019). However, these
methods cannot remove minimal amounts of harmful toxins in water. Therefore, there is a need
to develop more sensitive and practical techniques for water remediation. Nanotechnology provides
advanced methods for completely removing contaminants in water using nanomaterials (Mondal
et al., 2023). At the nanoscale, materials exhibit excellent and distinctive characteristics including
a strong chemical reactivity, a high surface-to-volume ratio, significant physical/chemical stability,
high absorption capacity, and strong charge transfer ability compared to bulk material (Ealia &
Saravanakumar, 2017). These properties of nanomaterials are leading to significant improvements in
efficiency for sustainable wastewater treatment. Due to their small size, nanomaterials easily penetrate
deep and remove contaminants from water.
Nanomaterials also aid in fabricating more efficient and advanced water filtration membranes,
allowing for permeability control and fouling resistance. Recently, highly reactive nanomaterials have
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97Function of nanomaterials in the treatment of emerging pollutants inwastewater
been thought to be unique and the best solutions for wastewater treatment, as they offer prospective
properties that would make them more efficient in providing pure and toxic-free water (Xu et a l.,
2023). There are many types of nanomaterials have been synthesized. Nanomaterials can be generally
classified into two categories: (i) carbon-based nanomaterials and (ii) metal/metal oxide-based
nanomaterials. Figure 6.1 shows different types of nanomaterials.
Carbon has been the primary source of water filtration and purification since antiquity in the
form of wood charcoal. Carbon allotropes such as fullerene, CNT, and graphene are attracting
interest from researchers in current technology because of their quick mechanisms, such as
adsorption, filtered membrane, photocatalytic oxidation, and sensing components (Gill etal., 2023).
Carbon remains a popular alternative for water treatment. On the other hand, the possibility of
metal and metal oxide-based nanoparticles for wastewater treatment has attracted many academics
and technologists. Metal-based nanomaterials have extraordinary qualities such as a high aspect
ratio, atomically accurate pores, a wide range of functionality, and high absorption activity (Deng
etal., 2023).
6.2.1 Carbon-based nanomaterial
Carbon-based nanoparticles are utilized to detect and remove water contaminants broadly. To improve
and develop water treatment, a wide array of carbon-based nanomaterials has been used.
6.2.1.1 F u l l erene
Fullerene (C60), known as Buckminsterfullerene, is a carbon-based compound with 60 carbon
atoms. sp2 hybridization holds all carbon atoms together, forming a hollow spherical shape. By
adding and attaching functional groups to the surface of fullerene, many kinds of fullerene may be
created. Fullerenes can be used as filter membranes, adsorbents, and biofilm-resistant surfaces in
water treatment engineering. The use of fullerenes in combination with ultraviolet (UV) irradiation is
the most modern and advanced disinfection procedure (ADP) for contaminant elimination (Ealia &
Saravanakumar, 2017).
6.2.1.2 Carbon nanotubes
Carbon nanotubes (CNT) are one-dimensional cylindrical structures formed by a honeycomb lattice
of carbon atoms. It has lengths ranging from a few micrometers to many centimeters with diameters
as small as 0.7 nm. Carbon nanotube ends can be empty or closed with a half-fullerene molecule.
There are two varieties of CNTs based on the number of layers: (i) Single Walled Carbon Nanotubes
(SWCNTs), which have a single layer of carbon atoms in cylindr ical shape, and (ii) Multi Walled Carbon
Figure 6.1 Structure of different types of nanomaterials.
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98 Detection and Treatment of Emerging Contaminants in Wastewater
Nanotubes (MWCNTs), which have more than one or two layers of carbon atoms in cylindrical form.
Physical and chemical approaches can be used to create CNT (Parveen etal., 2017), and physical
procedures at high temperatures result in large-scale CNTs. Due to the hollow cylindrical geometry of
CNTs, it is most widely used to remove contaminants and other organic contaminants from aqueous
solution through adsorption.
6.2.1.3 Graphene
Graphene is a two-dimensional planar sheet of hexagonally organized carbon atoms one atom thick.
It is a carbon allotropy with good capabilities for eliminating pollutants in an aqueous medium as a
selective membrane. Graphene also has promising qualities for wastewater treatment as an adsorbent
for the rapid and active removal of heavy metal ions in water. Graphene may be synthesized using
ordinary scotch tape and the Hammer method (Lingamdinne et al., 2016). Graphene oxide (GO)
is a functionalized graphene created by a graphite sheet’s chemical oxidation. The addition of this
functional group as oxide improves heavy metal adsorption overall.
6.2.2 Metal/metal oxide-based nanomaterials
Metal and metal oxide nanomaterials are effectively associated with developing a more efficient,
eco-friendly, cost-effective, and reliable water filtration process. Membrane technology is also going
on to its advanced stage by using metal and metal oxide nanomaterials. Different type of metal
nanoparticles has been synthesized for wastewater treatment. Silver, gold, copper, and iron are
frequently used in developing filtration membranes, nanosensors, and nano adsorbents to detect and
remove water contaminates. In addition, zinc oxide (ZnO), iron oxide, titanium oxide (TiO2), tin oxide
(SnO2), are examples of metal oxide nanoparticles that are effectively utilized for the photocatalytic
decomposition of contaminants in water (Rashid etal., 2014). These metal oxide NPs are considered
significant components in developing a more simple, easy, and accurate treatment process, that is,
photocatalysis among the advanced wastewater treatment.
6.3 SYNTHESIS AND CHARACTERIZATION OF NANOMATERIALS
Nanomaterials can be developed through a variety of techniques. These techniques can be roughly
divided into two categories: top-down and bottom-up. Figure 6.2 shows the different synthesis methods
for these two types.
6.3.1 Green synthesis of nanomaterials
The main goal of all technological advancements is to improve human comfort without jeopardizing
health. For this innovative cause of safety, an advanced and environmentally friendly development
technique is necessary. Sustainable development is also a big component of this since it involves
increasing the living system for all by not disrupting our ecosystem. Green nanotechnology contributes to
sustainable development by synthesizing and using nanomaterials (Schulte etal., 2013). The synthesis of
nanomaterials by the green method is gaining the attention of researchers and technologists due to its non-
toxic, cost-effective, and eco-friendly nature. Green technology is very efficient and a major component of
sustainable development as it is a requirement of the next generation or the upcoming future.
The most common interpretation of ‘green’ is the production of nanomaterials using plant-
based ingredients. However, the application of non-toxic solvents in synthesizing highly effective
nanomaterials is covered by green technology, which is limited and inclusive. Additionally, because
they use less mass and more potent ingredients, products made using green processes are anticipated to
significantly contribute to preserving the environment and ecosystems (Centi & Perathoner, 2011). An
excellent way to eliminate adverse environmental effects is through green nanotechnology. Table6.2
shows the green synthesis of nanomaterials for different applications.
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99Function of nanomaterials in the treatment of emerging pollutants inwastewater
6.3.2 Characterization of nanomaterials
In the following section, the numerous techniques used to characterize nanomaterials have been
discussed extensively. These techniques can be integrated or used solely to conduct research on
an exclusive attribute. These techniques can be compared, considering their accessibility, cost,
accuracy, non-destructiveness, flexibility of use, and propensity to work with specific compounds
or materials.
Despite the several approaches presented here, each one undergoes a comprehensive assessment.
Microscopy-based techniques, such as SEM, TEM, and AFM, can be used to determine the size, shape,
and crystalline makeup of the nanomaterials. Other methods include UV–visible, X-ray, spectroscopy,
and Raman scattering techniques to determine the elemental and compositional elemental analyses
and the optical properties of nanomaterials (Parveen et al., 2022a, 2022b). Figure 6.3 is shown the
various characterization techniques to get complete information on nanomaterials.
6.4 NANOMATERIALS-BASED APPROACHES OF WASTEWATER TREATMENT (WWT)
With rapid industrialization, urbanization, and population growth, the generation of wastewater has
increased significantly, leading to environmental pollution and water scarcity issues. Conventional
wastewater treatment methods often fall short of effectively removing various pollutants, including
heavy metals, organic contaminants, and pathogens. In recent years, nanotechnology has emerged
as a promising approach for wastewater treatment due to the unique properties (physical, chemical,
and biological properties compared to their bulk counterparts) of nanomaterials that can address the
limitations of traditional treatment methods. These unique properties make nanomaterials highly
effective in treating wastewater. Various types of nanomaterials, such as nanoparticles, nanotubes,
nanofibers, and nanocomposites, have been explored for their applications in wastewater treatment.
When it comes to the mechanism involved in the nanomaterials-based approach for wastewater
treatment, several key processes come into play. These processes include adsorption, photocatalysis,
membrane filtration, and disinfection.
Figure 6.2 Representation of two kinds of approaches followed for the synthesis of nanomaterials.
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100 Detection and Treatment of Emerging Contaminants in Wastewater
(i) Adsorption: Adsorption is a fundamental mechanism utilized in wastewater treatment, and
it plays a crucial role in the removal of various contaminants from water. The adsorption
process involves the attachment of pollutants onto the surface of a solid material, known as an
adsorbent. Nanomaterials, such as activated carbon nanoparticles, metal oxide nanoparticles
(e.g., titanium dioxide, iron oxide), and carbon nanotubes, exhibit a high surface area and
porosity, allowing them to effectively adsorb and remove pollutants from wastewater. In the
context of nanomaterials-based wastewater treatment, nanomaterials with high surface area
and porosity are commonly employed as adsorbents (Ahmed etal., 2022).
(ii) The adsorption mechanism relies on the interactions between the adsorbent surface and the
contaminants present in the wastewater. Such interactions are largely classified into physical
(physisorption) and chemical (chemisorption) adsorption. Physical adsorption occurred due to
weak forces between molecules like van der Waals forces, hydrogen bonding, and electrostatic
interactions (Fanourakis etal., 2020). Nanomaterials with large surface area-to-volume ratios,
such as activated carbon nanoparticles, graphene, and metal oxide nanoparticles, exhibit
high physisorption capacity. The contaminants in the wastewater come into contact with
the adsorbent surface, and the weak forces between the adsorbent and contaminants allow
them to adhere to the surface (Fanourakis etal., 2020). Physisorption is particularly effective
Table 6.2 Green techniques involved for the synthesis of nanomaterials and their operating parameters.
S. No. NMs Synthesis Methods Synthesis Parameter References
1Au Chitosan as a reducing
agent
Trihydrate tetra chloroauric acid
(HAuCl4.3H2O), chitosan, glacial
acetic acid, distilled water, temp:
100°C, time:15 min
Barajas etal. (2019)
2Ag Leaf extract of Malachra
capitata (L.)
Silver nitrate (AgNO3), n-hexane,
Malachra capitata (L.), distilled
water, temp: 90°C, time: 24 h
Srirangam and Rao
(2017)
3Cu Capparis spinosa fruit Copper sulfate solution, Capparis
spinosa, ethanol, deionized water,
time: 24 h 20 min, temp: 60°C
Ebrahimi etal. (2017)
4ZnO Ecofriendly wet chemical
method
Zn (NO3)2, sodium hydroxide
(NaOH), distilled water, temp:
60°C, time: 2 h 10 min
Yadav and Sisodia
(2022)
5ZnO Using garlic skin Garlic skin, zinc chloride, sodium
hydroxide (NaOH), distilled water,
time: 25 h
Modi and Fulekar
(2020)
6TiO2Sol–gel method Titanium tetra iso prop oxide
[Ti (OCH(CH3)2]4, isopropanol
[(CH3)2CHOH], nitric acid (HNO3),
deionized water, temp: 60–80°C,
time: 9 h
Sharma etal. (2014)
7Graphene Various concentrations
of Tec om a stan s leaves as
reducing/capping agents
H2SO4, and 1 g of sodium nitrate
(ISO-CHEM).
time: 1 hr, temperature: 90°C
Mahmoud etal. (2022)
8CNTs Using pyrolysis technique Coconut and olive oils are used
as precursors and acetone, nickel
chloride (5 wt%.) as a catalyst and
argon as a carrier gas.
temp: 900°C, time: 15 min
Hamid etal. (2017)
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101Function of nanomaterials in the treatment of emerging pollutants inwastewater
at removing organic chemicals such as dyes, pesticides, volatile organic compounds (VOCs)
and pharmaceuticals. The porous structure of nanomaterials provides many adsorption sites,
enabling them to capture and retain organic molecules effectively. Chemical adsorption
involves stronger chemical bonds between the adsorbent surface and the contaminants which
usually occurs through covalent or ionic interactions. Nanomaterials with specific functional
groups, such as metal oxide nanoparticles and zeolites, can undergo chemisorption with
certain contaminants. Chemisorption is especially useful in removing heavy metals and metal
ions from wastewater. These nanomaterials possess active sites on their surfaces that can form
strong chemical bonds with metal species, effectively immobilizing them. Additionally, ion
exchange processes may take place, where the nanomaterials release other ions (such as H+ or
Na+) into the wastewater while capturing the metal ions. Iron oxides (Fe3O4), TiO2, and zinc
oxides (ZnO) are the most widely used metal oxide-based nano-adsorbents for wastewater
treatment. Heavy metals like lead, chromium, arsenic, mercury, cadmium, nickel, and copper
could be eradicated from wastewater more efficiently by using nano-metal oxides compared
to activated carbon. TiO2’s appealing adsorption capability can be indicated by the effective
removal of phosphate, nitrate, and methyl blue. Manganese oxide nanoparticles have found
Figure 6.3 Different characterization techniques used for the study of nanomaterials.
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102 Detection and Treatment of Emerging Contaminants in Wastewater
extensive application in the elimination of lead (II), arsenic, cadmium (II), and zinc (II) from
wastewater due to their substantial surface area (Ahmed e t a l ., 2022). In many cases, adsorbents
can be regenerated and reused, reducing the overall treatment cost. Techniques like desorption
using appropriate solvents or changing environmental conditions can release the adsorbed
contaminants from the nanomaterials, allowing them to be recycled. Also, adsorption can
complement other treatment processes, such as biological treatment or membrane filtration,
by removing specific pollutants that may not be effectively treated by those methods alone. By
harnessing the adsorption capabilities of nanomaterials, wastewater treatment can achieve
improved water quality and contribute to sustainable water management practices.
(iii) Photocatalysis: It is a process that utilizes light energy and a photocatalyst to initiate
chemical reactions that can degrade or transform pollutants in wastewater. The photocatalytic
mechanism involves several steps that take place on the photocatalyst’s surface (Ahmed etal.,
2022). A few nanomaterials have photocatalytic characteristics, especially semiconducting
metallic oxides like zinc oxide (ZnO) and titanium dioxide (TiO2). When exposed to ultraviolet
(UV) light, these nanomaterials generate electron-hole pairs, which initiate redox reactions and
produce highly reactive oxygen species (ROS) (Fanourakis et al., 2020). These ROS, such as
hydroxyl radicals, possess strong oxidative capabilities that can degrade organic contaminants
into harmless by-products. Photocatalysis is particularly effective in treating organic pollutants
and emerging contaminants, (i.e., personal care goods and pharmaceuticals) present in
wastewater. The photocatalytic process begins with the absorption of photons from a light
source, typically ultraviolet (UV) or visible light. Upon photon absorption, the photocatalyst
undergoes electronic excitation, resulting in the generation of electron-hole pairs. The excited
electrons leave behind positive-charged holes in the valence band as they transition from
the valence band to the conduction band. This electron-hole separation is crucial in order to
perform subsequent photocatalytic processes. The separated electrons (e−) and holes (h+) on
the photocatalyst surface can engage in redox reactions that interact with the adsorbed species
or dissolved pollutants present in the wastewater (Fanourakis etal., 2020). The reactions can
be classified as oxidation and reduction processes. (i) Oxidation: strong oxidative abilities allow
the h+ holes produced in the valence band to interact with water molecules or hydroxyl ions
(OH−) that are adsorbed on the photocatalyst surface, producing the highly reactive hydroxyl
radicals (•OH). These hydroxyl radicals are potent oxidizing agents that can attack and degrade
organic contaminants, breaking them down into smaller and less harmful molecules.
(iv) Reduction: Simultaneously, the photogenerated electrons (e−) in the conduction band can
reduce certain species, such as dissolved oxygen (O2), creating superoxide radicals (•O2−) or
hydrogen peroxide (H2O2). These reactive species can participate in further redox reactions,
facilitating the degradation or transformation of pollutants. The reactive oxygen species
(ROS) generated during the photocatalytic process, comprise highly reactive species such
as hydroxyl radicals (•OH), superoxide radicals (•O2−), and hydrogen peroxide (H2O2). These
species have strong oxidizing abilities and have the potential to efficiently reduce a broad
spectrum of contaminants. These ROS target the chemical bonds of organic compounds,
allowing them to break down into smaller, less harmful molecules like carbon dioxide (CO2)
and water (H2O). The photoc atalytic process i s continuous, with the re generated photocat alyst
being available for subsequent cycles. The photogenerated electrons and holes recombine,
or they can be scavenged by sacrificial agents present in the wastewater, preventing their
recombination and maintaining a continuous supply of active species for photocatalytic
reactions. TiO2, ZnO, Fe2O3, zinc sulfide (ZnS), zirconium dioxide (ZrO2), cadmium sulfide
(CdS), and tungsten trioxide (WO3) are the most commonly used photocatalysts. The
bandgap energy of TiO2 has been successfully lowered and the TiO2 adsorption from the UV
light zone has been red-shifted by doping TiO2 with Cr, Ag, Zn, Al, Mn, Co, Fe, Ni, Pt, Bi,
Pd, S, Au, and N. The presence of UV light increases the efficiency of photocatalysts (Ahmed
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103Function of nanomaterials in the treatment of emerging pollutants inwastewater
etal., 2022). An ordered mesoporous silica (SBA-15) molecular sieve loaded with TiO2 and
combined with zirconium nanophotocatalyst was reported to minimize reactive red X-3B by
96% in a study by Bai etal. (2020). Additionally, photocatalysis is environmentally friendly
as it utilizes light energy and does not require the addition of chemicals. However, challenges
such as catalyst stability, efficient utilization of solar energy, and optimization of reaction
conditions need to be addressed for large-scale implementation of nanomaterials in waste
water treatment.
(v) Membrane filtration: It is a widely used technique in wastewater treatment for the
separation and removal of suspended solids, particulate matter, microorganisms, and
dissolved contaminants. Membrane filtration operates on the principle of physical sieving.
The wastewater is passed through the membrane, and particles larger than the membrane’s
pore size are retained and accumulate on the feed side of the membrane. The clean permeate,
consisting of purified water and smaller dissolved molecules, passes through the membrane
and is collected. Membranes have different pore sizes and selectivity, which determine their
filtration capabilities. Nanofiltration and reverse osmosis membranes have even smaller pore
sizes (<0.001 µm) and can remove dissolved salts, ions, and small organic molecules. During
membrane filtration, fouling (deposition and accumulation of particles, microorganisms,
organic matter, and other contaminants on the membrane surface or within its pores) can
occur, leading to reduced filtration efficiency. Fouling can result in decreased permeate
flow, increased pressure requirements, and reduced membrane lifespan. Nanomaterials
are also employed in membrane filtration processes for wastewater treatment. Membranes
with nanoscale pores, such as nanofiltration (NF) and reverse osmosis (RO) membranes,
can effectively separate and remove dissolved salts, heavy metals, and other contaminants.
Nanomaterials, including carbon nanotubes, graphene oxide, and zeolites, are integrated
into membranes to enhance their selectivity, permeability, and fouling resistance. These
modified membranes offer improved water quality, higher water recovery rates, and
prolonged membrane lifespan. Periodic cleaning of the membrane such as backwashing,
chemical cleaning, or air scouring is necessary to remove fouling and maintain optimal
filtration performance.
(vi) Disinfection: Disinfection is an essential step in wastewater treatment to ensure the removal
or inactivation of harmful microorganisms, including bacteria, viruses, and protozoa.
Disinfection processes often involve the use of strong oxidizing agents, such as chlorine
(Cl2), chlorine dioxide (ClO2), ozone (O3), or hydrogen peroxide (H2O2) (Ahmed etal., 2022).
These oxidants work by reacting with the microorganisms’ cellular components, including
proteins, enzymes, and nucleic acids. The oxidation disrupts the microorganisms’ structure
and metabolic processes, leading to their inactivation or death. Oxidizing agents can penetrate
the cell walls or membranes of microorganisms. Once inside, they cause damage to the
lipid bilayer, resulting in the disruption of the cell’s integrity. This leads to the leakage of
cellular contents and the loss of essential functions, ultimately leading to the inactivation of
the microorganisms (Fanourakis etal., 2020). Oxidizing agents can also directly damage the
genetic material (DNA and RNA) of microorganisms. They induce structural modifications
and breaks in the DNA or RNA strands, preventing replication and transcription processes.
Disinfectants can denature proteins by breaking the hydrogen bonds, disulfide bridges, and
other non-covalent interactions that maintain the protein’s native structure. This denaturation
disrupts the protein’s functional properties, leading to the loss of enzymatic activity and
vital cellular processes. Without functional proteins, microorganisms are unable to carry out
essential metabolic functions, resulting in their inactivation. Some disinfection processes, such
as chlorination or ozonation, produce reactive oxygen species (ROS) as by-products. These
ROS, including hydroxyl radicals (•OH) and superoxide radicals (•O2−), are highly reactive
and can damage cellular components, including proteins, lipids, and DNA. The ROS attack
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104 Detection and Treatment of Emerging Contaminants in Wastewater
the microorganisms’ cellular structures and biomolecules, leading to their inactivation.
Nanomaterials have shown potential for disinfection purposes in wastewater treatment. Silver
nanoparticles (AgNPs) and copper nanoparticles (CuNPs) possess antimicrobial properties,
making them effective in inactivating bacteria, viruses, and other microorganisms present in
wastewater. The nanoparticles release metal ions that interact with microbial cell membranes,
leading to cell damage and death. In addition to MWNTs, Pseudomonas aeruginosa PAO1 has
been successfully inhibited by AgNP coating (Kim etal., 2018). Similar results were obtained
with ZnO nanocrystal-doped 3D nano-customized silicon (Si)-wafers against E. coli, one of the
most prevalent organic pollutants in wastewater (Rahman etal., 2021). CuONPs impregnated
with a mixed matrix of PES and cellulose acetate showed a 75% inhibition in another green
synthesis process utilizing copper (Singh et al., 2021). Additionally, nanomaterials like
graphene oxide have been explored for their ability to generate reactive oxygen species upon
exposure to light, providing disinfection capabilities through a photocatalytic mechanism.
6.5 ADVANCES IN TERMS OF GREEN APPROACH FOR THE LARGE-SCALE USE OF
NANOMATERIALS IN WASTEWATER TREATMENT
Nanotechnology has several physical, chemical, and biological processes for cleaning water. These
include membra ne separation, adsorption, ion exchange, chemical precipit ation, photocata lyst splitt ing
and bioremediation using various nanomaterials. In light of the potential for eliminating adsorptive
material and subsequent metal(loid) extraction, adsorption-based approaches are acceptable. Carbon-
based nanomaterials such as CNTs, graphene and fullerene may be employed for adsorption. The
technique of using nanoparticles or nanomaterials to remove environmental contaminants from
contaminated areas is known as nano-remediation. Metal/metal oxide-based nanomaterials such as
TiO2, ZnO, SnO2, and silver (Ag), Gold (Au) and lead (Pb) nanoparticles are successfully used to
eliminate metal(loid)s and other contaminants in wastewater treatment (Hairom etal., 2021). Hence,
nanomaterials have emerged as the most effective strategy for clean-up due to their increased features,
such as a high surface-area-to-volume ratio and strong reactivity.
In the next section, we will focus on four main categories of nanomaterials in wastewater treatment
applications as shown in Figure 6.4. These include nano-adsorbents, nano-catalysts, nanofiltration
membranes and nanosensors integrating the nanotechnologies as mentioned earlier with advanced
processes.
6.5.1 Nanofiltration
Generally, the process of removing contaminated particles from water using a porous membrane is
known as filtration. This porous membrane traps the contaminated particles on their surface. If the
membrane h as the size of por es in the nanos cale range, t hen nanofiltr ation process oc curs. Nanofi ltration
refers the excellent combination of uniform nanopores membrane with a unique ability to remove
hardness, total dissolved solids and also microorganisms. Based on pore size, there are four main types
of separation membranes have been developed, including nanofiltration (NF), microfiltration (MF),
ultrafiltration (UF), and reverse osmosis (RO) membranes. The pore sizes of NF membranes are less
than 1–2 nm, which are the smallest ones and much smaller than those of MF and UF membranes. Due
to its small pore size, it can be easily employed to filter water pollutants very efficiently at the minute
level. Hence, nanofiltration is the most effective and widely used technique in water quality treatment
because of its advanced filtration mechanism and applicability for removing nano pollutants.
Carbon nanotube-based filtration membranes display excellent properties due to its nanoscale-
porosity. Many studies on the CNTs-based filtration process have been reported in the last decades.
Vertically aligned (VA) and mixed matrix (MM) CNT membranes are the two types of nanotube
membranes that are based on existing manufacturing technologies (Ahn etal., 2012). Fluid can only
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105Function of nanomaterials in the treatment of emerging pollutants inwastewater
enter through the hollow interior of the CNT or between the bundles of CNTs because of how the
CNTs are organized in the VA-CNT membranes. By matching perpendicular CNTs with a supporting
filler material (epoxy, silicon nitride), the VA-CNT membranes may be created between the tubes
(Hinds etal., 2004).
On the other hand, a mixed matrix (MM) CNTs membrane is made up of many layers of polymers
or another composite material. Due to the frictionless ability of CNT to transfer water through
hydrophobic hollow cavity nanotubes, such membranes work with minimal energy consumption. The
membrane is highly susceptible to many salts and contaminants, being self-cleaning, reusable, and
good water.
Nanocomposite membranes made of PVDF/poly(styrene-butadiene-styrene)/thiocyanate and
silver-modified MWCNTs have been created by solution blending (Mehwish etal., 2015). The spray-
assisted layer-by-layer method was employed by Liu etal. (2013) to construct the PES/functionalized
MWCNT (F-MWCNTs) membrane. N, N-dimethylacetamide (DMAc) was employed by Shawky etal.
(2011) to create MWCNT/aromatic PA nanocomposite membranes using a polymer grafting process.
MWCNTs/polyaniline (PANI)/PES membranes were used by in-situ polymerization, according to Lee
etal. (2016). The absence of reactants in the raw material makes in-situ polymerization stand out from
other processes. Instead of taking place on both sides of the interface between the continuous phase
and core material, all polymerization occurs in the continuous phase, as in interfacial polymerization.
The in-situ colloidal precipitation production of the oxidized MWCNTs (OMWCNTs)/graphene oxide
(GO)/PVDF membrane was described by Ho etal. (2 017).
Figure 6.4 Remediation techniques using nanomaterials for the treatment of wastewater.
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106 Detection and Treatment of Emerging Contaminants in Wastewater
6.5.2 Nano adsorbents
The nano adsorption process refers to the adsorption of water contaminants on the surface of
nanoparticles. Nano sorbents are nanomaterials that absorb water contaminants such as heavy
metal ions and organic and inorganic impurities. Nano-sorptions are now regarded as a developing
remediation str ategy for the elimination of water contam inants in order to produce pu re drink ing water.
Furthermore, these have garnered additional attention due to their unique properties and potential
as a viable alternative to conventional adsorbents. Technologists and researchers have documented
coagulation’s effect on the adsorption activity of carbon-based nanomaterials. More recently, various
research studies suggested that nano sorbent materials have excellent and quite promising properties
for water purification and remediation, including carbon nanotube, graphene, fullerene, polymers,
and metal and metal oxides nanosorbents (Nasrollahzadeh etal., 2021).
Burakov etal. (2018) compared the general heavy metal adsorption potential of CNTs with several
conventional materials. It has been suggested that plasma-oxidized multiwalled CNTs rather than
chemically oxidized multiwalled CNTs might be employed as adsorbents for specific metals. The
presence of functional groups containing oxygen on the CNT surface gave plasma-oxidized tubes
better adsorption performance than chemically oxidized CNTs. Experimental findings demonstrate
that plasma-oxidized CNTs tend to desorb metal ions more readily (Burakov etal., 2018).
6.5.3 Photocatalysis
This photocatalysis remediation significantly benefits eliminating trace contaminants in aqueous
solution due to its low cost, environmental friendliness, and universal applicability. Fast-developing
technology has moved this procedure to the forefront of the sustainable wastewater treatment strategy.
Photocatalysis is a most demanded and well-established technique for water pollutant degradation by
UV-oxidation-based water splitting (Lazar etal., 2012). In simple words, Photocatalysis refers to ‘the
splitting of the water by absorption of light’. It is used to quickly break down various pollutants such
as organic materials, pesticides, dyes, and so on. Due to its vast variety of applicability, Photocatalysis
with nanoparticles as catalysts is utilized to enhance the water quality by removing the comminates.
In this context, metal oxide nanoparticles are widely used for water purification as practical
elements of photocatalysts. TiO2 and ZnO NPs have been synthesized by green methods and analyzed
as photocatalysts for water treatments (Li etal., 2012).
Recent research has demonstrated the excitement of CNTs to TiO2 nanoparticles. It has been
demonstrated that reduced photoluminescence strength caused by a reduced recombination load
indicates enhanced photocatalytic oxidation efficiency of CNT/TiO2 composites to phenol. Single-
walled carbon nanotubes (SWCNTs) are more able to increase the photocatalytic activity of TiO2 than
MWCNTs because they have more direct contact with the surface of the TiO2 nanoparticles. At the
interface between SWCNTs and TiO2, indium tin oxide (ITO) thin films have also been applied. This
considerably impacted the photoelectrochemical behavior and reduced the resistance between the
two layers (Duong etal., 2011).
6.5.4 Nano sensors
The surface water has been contaminated by household and industrial garbage exposure, which might
lead to significant aquatic life diseases. Because of the low concentrations of toxins in water bodies, small-
scale monitoring of these dangerous pollutants has become critical. Researchers are becoming interested
in nanomaterial-based sensors for detecting water pollutants at low concentrations in this context.
Nanosensors are device that produces fast responses towards any change in the surroundings.
Change may be in the form of light, heat, temperature, or change in volume concentration as input
signal and are used to convey the information about the behavior as output signal. Nanosensors can
sense the analyte at low detection limits, high selectivity, sensitivity, and long-term stability. Due to its
low detection limit and fast response, it is w idely used for advanced water t reatment. These nanosensors
are developed using nanomaterials such as carbon nanotubes, graphene, fullerene, metal, and metal
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107Function of nanomaterials in the treatment of emerging pollutants inwastewater
oxide Nanomaterials, possessing high surface-area-for fast reactivity and binding affinity to target
molecules even at very low concentrations, which produce a fast response. Integrating nanosensors
in the conventional water quality sensor may enhance treatment efficiency because nanosensors have
contributed excellent performance in removing contaminants in wastewater.
Nanosensors have been designed for water quality monitoring, including optical sensors, surface
plasmon re sonance, calor imetric , electrochemic al sensors , and surf ace-enh anced Rama n spectros copic
sensors (Parveen etal., 2022a, 2022b).
It is genera lly safe to ut ilize CN Ts as a n electrode in bios ensor application s. Rarely, the CN T electrode
interacts directly with water, and however, some risk measurements may be observed. First off, 2D
NMs, particularly graphene, are frequently combined with 1D CNTs for excellent electroconductivity
and mechanical strength. These macro frameworks provide a variety of environmental concerns and
differ in their physicochemical properties, all of which require careful consideration (Georgakilas
et al., 2015). Electrochemical biosensor applications frequently use CNTs functionalized with poly
diallyl dimethylammonium chloride, or (PDDA) (Zhang etal., 2011).
Adopting revolutionary advanced water technologies to provide high-quality drinking water
with an improved ability to reduce micropollutants is critical. Water treatment technologies that are
flexible and adaptive must be used to boost industrial production processes. Compared to traditional
water treatment technologies, one of the most significant qualities of nanoparticles is their ability to
combine diverse properties, creating multifunctional systems like nanocomposite membrane that is
capable of holding particles and removing contaminants. Nanomaterials can also help to improve
process efficiency because of their unique features, such as their huge surface area.
6.6 BARRIERS ASSOCIATED AND ENVIRONMENTAL CONCERNS OF
NANOTECHNOLOGIES
Although nanotechnology has great implications in wastewater treatment, due to its detrimental
impact on humans, the aquatic ecosystem, and the environment as a whole, they are frequently seen
as problematic when they are released from the treatment system to the environment after use. There
is a lack of understanding and information on the nanomaterials (NMs) fate, behavior, and toxicity
upon exposure to humans, aquatic ecosystem, and the environment; therefore, it is critical to gain
more knowledge in this area. Limited information about the aggregation and deposition of particular
NMs due to the limitation of standard methods and instrumentation for their monitoring and
detection poses a major barrier/ challenge for the use of nanotechnologies in wastewater treatment.
The same properties such as shape, small size, high reactivity and many more which are useful for
treating industrial wastewater become a hazardous problem for the environment. It is necessary
to thoroughly study the dose–response impact and the resulting exposure pathways in order to
comprehend the risk assessment of NMs. It has been suggested that the effects on lower organisms
should be investigated because they are an essential part of the food chain (Patil etal., 2016). Among
all the nanomaterials, nanoparticles (NPs) are considered for having the most detrimental effects on
the aquatic ecosystem, human health, and the environment. Most NPs do not cause instant death, but
they do have an extensive range of harmful effects. For example, silver nanoparticles, titanium dioxide
nanoparticles (TiO2), carbon nanotubes (CNTs), and so on. TiO2 NPs have been reported to cause
the formation of reactive oxygen species (ROS), necrosis, mutagenesis, lipid peroxidation, apoptosis,
changes in cell morphology, and mitochondrial dysfunctioning. The physicochemical properties of
the NPs (size, morphology, aggregation, reactivity, surface charge, and dissolution) along with the
intra and extracellular environment are the key regulators of their toxicity (Thangadurai eta l ., 2020).
In 2010, The American Environmental Protection Agency published the effects of TiO2 NPs on a
variety of aquatic life such as bacteria, algae, plants and fish, and invertebrates. Depending on the
concentration and exposure time, various effects were recorded like pathological alterations in the
gills, respiratory distress, reduced reproductive output in Daphnia, and behavioral abnormalities
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108 Detection and Treatment of Emerging Contaminants in Wastewater
in fish (Khan etal., 2021). Zerovalent iron (nZVI) has been proven to be toxic to Escherichia coli,
Bacillus subtilis var. niger, and Pseudomonas fluorescens and increased the production of ROS in
their cells. The nZVI has also been reported to cause phytotoxicity and accumulation, reduction in
transpiration and growth of hybrid poplars (Populous deltoids × Populous nigra) and cattail (Typha
latifolia) plants (Patil etal., 2016). The CuO NPs cause oxidative stress in fishes even upon short-
term exposure. Additionally, they have been found to enhance the activity of different oxidative
enzymes including superoxide dismutase (SOD), glutathione S-transferases (GST), and catalase
(CAT) in various organs (gills, livers, and kidney) and due to overproduction of ROS and disturbs
homeostasis (Thangadurai etal., 2020). Further, in order to better understand the ecotoxicological
effects of NMs, there is a need to study not only their environmental effects but also their genotoxic
effects and their effects at molecular levels. The nanomaterials are very beneficial to the industries for
the wastewater treatment; therefore, it is essential to focus the research on the systemic release and
monitor their effects to protect from their ecotoxicity. In this concern, the optimization and design
of nanotechnology-based wastewater treatment require a thorough knowledge of the structure–
activity of nanomaterials. This will help suggest the material selection, structural integrity, improve
durability and process reliability. More green synthesis and eco-friendly approaches will also work
to help in this direction
6.7 FUTURE PERSPECTIVES OF NANOMATERIALS IN WASTEWATER TREATMENT (WWT)
Although there are related challenges but breakthroughs in the realm of nanotechnology are
associated with the advancement of wastewater treatment technologies. Since the preceding
decade, NMs have been widely used in the wastewater treatment industry. Due to the specific
physicochemical properties of these materials, including their size, structure, durability, reactivity,
mobility, surface-to-volume ratio, and others, they have several advantages over other treatment
technologies for emerging pollutants from wastewater, including faster kinetics, higher efficiency,
selective affinities for specific pollutants and remarkable antimicrobial activity. There is so much
research going on in various nanotechnology areas; for instance, nanomembrane filtration, nano
photocatalysts, nano sorbents, and nanomotors to maximize the efficiency of the process. The
synthesis of nanocomposites is another potential area to facilitate the dispersion capability and
stability of NMs during the reaction. The green synthesis approach for the formation of NMs using
biological life forms has attracted a lot of attention in the past few years in order to overcome the
toxicity of the NMs. Due to the presence of various structures of the oxides available for metals and
the diversity of the biological life forms, a detailed investigation in this research area will prove to
be very helpful in overcoming the challenges of the wastewater treatment sector (Hoseinpour &
Ghaemi, 2018). However, the development of safe and inexpensive nano-engineered materials opens
up many opportunities for novelties in the near future, especially for the decentralized treatment
systems, heavily degradable contaminants, and point-of-use devices. Furthermore, cutting-edge
analytical and imaging technologies can be beneficial for the analysis and measurement of nanoscale
objects, particularly for water treatment processes. The overall cost-effectiveness of the advanced
technologies over conventional technologies needs to be understood for large-scale implications
of NMs in the treatment of wastewater. Regardless of substantial advancements in the use of NMs
for wastewater treatment, “real-time monitoring models” are essential for ensuring the efficacy
and effectiveness of the NMs in the treated water while developing a better understanding of the
performance of nanotechnology in the treatment process. Additionally, in order to mitigate the
health and environmental concerns associated with NMs in this industry, several national and
international regulations should be proposed and implemented critically. Only then, they can be
adaptable to a large-scale treatment process. All the research communities working in this sector
should follow proper guidelines and regulatory standards to reduce the eco-toxicity effects of NMs
in the future (Ahmed etal., 2022).
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109Function of nanomaterials in the treatment of emerging pollutants inwastewater
6.8 CONCLUSION
Nanomater ials-based approaches provide innovative solutions for addressing the challenges associated
with wastewater treatment. The unique properties of nanomaterials enable enhanced adsorption,
photocatalytic degradation, membrane filtration, and disinfection of pollutants in wastewater. It
is of critical importance for the development of modified nanomaterials, their oxides, and hybrid
nano-based frameworks for tackling waste-water treatment problems. To ensure long-term viability
and sustainability, it is crucial to use appropriate and affordable nanomaterials for the waste-water
treatment process. Nanomaterials are very effective because of their high reactivity, yet they still
have several drawbacks which need to be rectified. One of the major hurdles in implementing
nanomaterials is the potential health risks linked with their toxic effects. One promising way to
enable acceptable nanomaterial applications is the production of nanocomposite materials consisting
of functional polymers and inorganic solids. With further research and development, nanomaterials
have the potential to revolutionize the field of wastewater treatment and contribute to sustainable
water management practices.
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(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0113
Rayane Kunert Langbehn*, Felipe Matheus Müller, Elisângela Edila Schneider,
Camila Pereira Senna, Eric Sanches-Simões, Júlia Pedó Gutkoski, Maikon Kelbert,
Camila Michels and HugoMoreira Soares
Department of Chemical Engineering and Food Engineering, Federal University of Santa Catarina, Florianópolis, Santa Catarina
88040-900, Brazil
*Corresponding author: rayane.kunert@posgrad.ufsc.br
ABSTRACT
The presence of emerging contaminants (ECs) in super ficial and drinking water is a reality worldwide. Among them,
we can highlight compounds such as personal care products and pharmaceuticals used to treat and prevent human
or animal diseases. ECs end up in the environment mainly because of inefficient wastewater or sludge treatment.
It is well known that conventional treatment does not completely remove these substances. In addition, ECs pose
a potential risk if released into the environment because of their toxicity, recalcitrance, and biouptake in animals
and plants. This chapter will cover biological and physicochemical treatments to remove EC from wastewater and
sludge. We will address the most recent advances for each process, focusing on their main parameters, operation
conditions, and applications. Moreover, we will compare the advantages and disadvantages of each process.
This chapter provides a comprehensive understanding of the role of biological and physicochemical processes,
applied individually or combined, in treating wastewater and sludge containing EC. Lastly, we will present future
perspectives to improve the treatment of ECs in wastewater treatment plants.
Keywords: biological processes, degradation, micropollutants, operating conditions, physicochemical processes
7.1 INTRODUCTION
Urbanization and industrialization in the last decades have increased the demand and use of chemicals
in the agriculture, health, and technology sectors. These development processes have promoted
several advances, including increasing life expectations and quality. However, this paradigm shift
has also introduced several anthropogenic chemical substances into the environment. Recently,
the presence of emerging contaminants (ECs) – also known as emerging micropollutants, organic
micropollutants, emerging pollutants, and contaminants of emerging concern – in the environment
has attracted attention and raised concern (Besha et al., 2017; Dharupaneedi et al., 2019). These
Chapter 7
Treatment approaches for emerging
contaminants in sludge and
wastewater
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114 Detection and Treatment of Emerging Contaminants in Wastewater
xenobiotic compounds are recognized as pollutants, in their majority, because of their potentially
harmful effect on human health and the environment (Alvarino etal., 2018; Dubey etal., 2021).
ECs are found in the environment and wastewater treatment plants (WWTPs) at concentrations
ranging from nanograms per liter to micrograms per liter (Couto et a l., 2019). They are classified
according to their source and characteristics (Peña-Guzmán et al., 2019). Some common groups
include: (i) pharmaceuticals (e.g., antibiotics, analgesics, and antidepressants); (ii) personal care
products (PCPs) (e.g., shampoos, soaps, perfumes, cosmetics, and oral care products); (iii) hormones
and similar molecules; (iv) hydrocarbons (combustion of molecules which release polycyclic aromatic
hydrocarbon); (v) food additives (synthetic molecules such as sweeteners and antioxidants); (vi)
transformation products (TPs) of pharmaceuticals by the human or animal body; and (vii) pesticides.
The fir st mention of ECs dates back to the last decades of the 20th century. In the 1970s, Hi nes (1979)
reported the presence of pharmaceutical substances in the environment. Ever since, the spread of ECs
and concerns around this matter have arisen. All ECs present a substantial risk to the environment;
however, their long-term effect is still unknown. Moreover, once they reach the environment, EC
might persist for long periods, bioaccumulate in the food chain, and affect biodiversity (Khan etal.,
2020; Rempel etal., 2021).
Several examples of the rising EC bioaccumulation in different environments and its influence on
the food chain can be found in the literature. Guillette et al. (1994) reported that juvenile alligators
living in contaminated lakes in Florida exhibited abnormal levels of hormones because of exposure to
dicofol and DDT pesticides. These ECs deregulated the endocrine system, affecting the reproductive
system and causing the population to decline. Later on, during the 2000s, the vulture population
in Pakistan decreased by over 95%. Their death was caused by renal failure because of the anti-
inflammatory drug diclofenac, ingested through the food source of dead domestic livestock (Oaks
et al., 2004). Moreover, despite the banishment of polychlorinated biphenyls, Jepson et al. (2016)
demonstrated that European cetacean species continue to have high concentrations of these ECs.
According to this study, polychlorinated biphenyls induced reproductive toxicity, causing the long-
term population 0 and suppressing cetaceans’ population recovery.
Similar to other living beings, the effect of ECs on human health is also a concern because of their direct
and indirect risks. Indirectly, exposure to some ECs (e.g., antibiotics) might contribute to the occurrence
of antimicrobial resistance genes in bacteria, generating superbugs (Wang et al., 2020). Furthermore,
human exposure to EC might also have a harmful direct effect on human health, but the knowledge
of long-term exposure to EC in low concentrations is still unknown. Studies indicate that ECs, such as
endocrine disruptors, might be related to hormonal disruptions and increased cancer risk in humans
(Starling etal., 2018). A major exposure route cited by authorities and the academic community that can
lead to human contamination is the presence of ECs in drinking water. Therefore, facing this imminent
risk requires that both remediation practices for already-contaminated environments and new alternative
substitutes to replace synthetic recalcitrant chemicals become the focal points of future studies.
Regarding remediation practices, it is crucial to implement effective measures to remove ECs from
contaminated carriers, such as wastewater and sludge, before their discharge. These implementations
require studies on the fate of ECs in W WTPs and parameter optimization for efficient removal. This
chapter will cover the removal of ECs through several biological and physicochemical processes for
sludge and wastewater treatment (F i g ure 7.1). For each process, its pros and cons, principal operating
conditions, and applications will be presented. Lastly, we will cover the perspectives for EC removal
in W WTP.
7.2 BIOLOGICAL PROCESSES
Biological processes rely on microbial activity to remove conventional contaminants and ECs in
WWTP. These processes have been used for decades to treat diverse types of waste, for example,
municipal, industrial, and agricultural. This versatility of bioprocesses stands out because they usually
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115Treatment approaches for emerging contaminants in sludge and wastewater
require mild operating conditions (e.g., temperature, pressure, and pH), implying less energy and
chemical inputs. Moreover, some bioprocesses are applied for resource recovery, generating fuels,
fertilizers, and other valuable substances from renewable waste.
The primary goal of bioprocesses in WWTP is to remove organic matter and nutrients. Although
ECs have a complex structure, they might also be removed by bioprocesses in WWTP. However, the
removal efficiency will depend on the ECs physicochemical properties, operating conditions, and
the microbial community (Langbehn et al., 2021). Microorganisms may use several mechanisms to
remove ECs from wastewater and sludge, as depicted in Figure 7.2. Depending on the microorganism
community and the EC, these mechanisms can occur together or separately.
Biodegradation is the most common removal mechanism observed in bioprocesses; it is mediated
by enzymes and may occur in the extra or intracellular medium. External biodegradation occurs
through enzymes secreted by microorganisms (F ig u re 7. 2 f ). Conversely, internal biodegradation
(Figure7. 2 e) uses intracellular enzymes and requires an additional step of bioadsorption (Figu re7. 2b)
to transfer the EC to the intracellular medium. In the intracellular medium, TPs can either follow
the bioaccumulation or biouptake processes on their original structure or after their biodegradation.
TPs can also return to the extracellular medium through vesicles. Sometimes, side mechanisms, like
photolysis and oxidative degradation, assist biodegradation by partially degrading ECs (Fig u r e s 7. 2 a
and 2c) (Gondi etal., 2022; Oberoi etal., 2019).
EC biodegradation occurs via metabolic and co-metabolic pathways, which are determined by EC
concentration (Alvarino etal., 2018). The metabolic pathway uses EC as the sole carbon and energy
source for microorganisms. Conversely, in the co-metabolic pathway, EC biodegradation is dependent
on primary substrate degradation. The primary substrate degradation allows microbial growth,
Figure 7.1 Biological and physicochemical treatment approaches for ECs in sludge and wastewater.
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116 Detection and Treatment of Emerging Contaminants in Wastewater
induces enzyme production, and acts as a source of electron donors for EC biodegradation (Alvarino
etal., 2018; James & Vijayanandan, 2023). However, the low concentrations of ECs in wastewater
do not provide the required energy for its use as a primary substrate; therefore, their biodegradation
occurs mainly via the co-metabolic pathway (Alvarino etal., 2018).
Adsorption is a frequently reported pathway for EC removal in bioprocesses (F i g ur e 7. 2 h). It
occurs through physicochemical interactions between EC and microorganisms or extracellular
polymeric substances (EPS). After adsorption in EPS, biodegradation may occur through the action
of extracellular enzymes (Figure 7.2g) (Oberoi etal., 2019).
During biological processes, the role of ECs in WWTPs will depend on their capability to be
sorbed (absorption or adsorption) for both sludge and wastewater treatment (Besha et al., 2017).
When the ECs are ionizable in the medium, adsorption occurs by electrostatic attraction to other
surfaces, as indicated by the acid dissociation constant (pKa) (e.g., positively charged groups interact
by electrostatic forces with microorganism surface cells that are negatively charged) (Mai et al.,
2018). Conversely, the absorption of ECs happens through hydrophobic interactions. Hydrophobic
functional groups interact with the lipid fractions in the medium. In these cases, the octanol–water
partition coefficient (KOW ) value is a crucial parameter (Zhang etal., 2013).
By understanding the removal mechanisms of EC during biological wastewater treatment, it is
possible to evaluate and propose new approaches for effective EC removal from solid and liquid wastes
in WWTP. The following sections will elucidate the pros and cons of the most commonbioprocesses in
a non-exhaustive way. First, we describe the features of conventional processes – technologies already
available for industrial implementation and used in WWTP; then, we present non-conventional
processes – technologies that are not yet well-established for WWTP (Figure 7.3).
Figure 7.2 General EC removal mechanisms in a generic cellular structure: (a) photolysis, (b) bioadsorption,
(c)oxidative degradation, (d) biouptake/bioaccumulation, (e) internal biodegradation, (f) external biodegradation,
(g)adsorption and biodegradation, and (h) adsorption.
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117Treatment approaches for emerging contaminants in sludge and wastewater
Figure 7.3 Conventional and non-conventional bioprocesses used to treat wastewater and sludge: (a) activated
sludge, (b) anaerobic digestion, (c) bioelectrochemical systems, (d) composting, (e) membrane bioreactor, and (f)
wetlands.
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118 Detection and Treatment of Emerging Contaminants in Wastewater
7.2.1 Conventional
7.2.1.1 Activated sludge
Activated sludge processes, both conventional activated sludge (CAS) and granular activated sludge
(GAS), are key components of WWTP (Figure 7.3a). In both CAS and GAS processes, a diverse
microbia l community works to degrade organic mat ter. While these biological processes can contribute
to reducing any compound classified as an EC, their efficiency in degrading ECs is not optimal and
can vary significantly (Burzio etal., 2022). This variation is influenced by factors such as the nature
of the contaminants and the operating conditions (i.e., aeration, temperature, pH, inhibitors, and
disturbances). For instance, ECs have been shown to persist through physical, chemical, and biological
treatment of wastewater (Castaño-Trias etal., 2021; Petrie etal., 2014).
The GAS process is a more recent development. In GAS systems, the microbial community forms
compact granules, which can enhance the degradation of ECs and improve process efficiency (Winkler
etal., 2018). The granular structure provides a favorable environment for the growth of specialized
microorganisms, which can degrade specific ECs resistant to conventional treatment processes (Wilén
etal., 2018).
However, while both CAS and GAS processes can reduce the concentration of ECs in wastewater,
they may not completely eliminate them. Specific recalcitrant molecules may resist degradation and
persist in the treated wastewater. The degradation pathways may also generate TPs that can also be
total or partially not degraded during the process (Wang and Wang, 2018). Therefore, further research
is needed to enhance the efficiency of these processes and to understand the fate of ECs during
treatment.
In the context of sludge treatment, both CAS and GAS are operationally applicable. However, the
fate of these contaminants in the sludge is a critical consideration. The EPS present in the sludge can
adsorb ECs, potentially retaining them in the sludge. This highlights the need for careful handling and
further investigation into the potential environmental and public health risks associated with sludge
disposal (Burzio etal., 2022; Petrie etal., 2014).
7.2.1.2 Membrane bioreactor
Membrane bioreactor (MBR) is a hybrid technology used in WWTP that combines mostly CAS
and membrane filtration for biodegradation and solid–liquid separation (Figure 7.3e). In MBRs,
microfiltration or ultrafiltration membranes are used to substitute the secondary clarifier of CAS.
Commercial MBR modules use flat sheet or hollow-fiber membranes in two configurations: (i)
submerged membranes (immersed into the biological tank) or (ii) external circulation (side-stream)
(Alvarino etal., 2018).
MBR is an alternative to CAS for final effluent quality improvement. A higher sludge concentration
can be employed during MBR operation and, consequently, a longer solids retention time (SRT),
resulting in a lower space requirement and reducing biomass production (Liu et al., 2022). Besides
that, MBR’s permeate presents high quality, and there is a complete decoupling of hydraulic retention
time (HRT) and SRT (Grandclément etal., 2017). However, MBR requires high energy consumption
for its operations (e.g., aeration used to minimize membrane fouling and pressurization for pressure-
driven membranes), and ECs are usually not fully removed (Besha et al., 2017). Recently, MBR has
gained attention because of the development of new processes that aim to reduce membrane cost and
energy consumption (Goswami etal., 2018).
Despite all these advantages, ECs are usually not fully removed in MBR. ECs removal mechanisms
by MBR have been widely investigated, which include size exclusion, volatilization, biodegradation,
and sorption (Goswami et al., 2018). Depending on the characteristics of ECs, different removal
mechanisms can occur: sorption in sludge for apolar and hydrophobic ECs, and biodegradation for
polar and hydrophilic ECs (Besha et al., 2017). Overall, the main removal mechanism couples the
sequence of those two (sorption followed by biodegradation), being directly dependent on operational
conditions (SRT, HRT, temperature, pH, redox conditions, and sludge concentration) (Xiao et al.,
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119Treatment approaches for emerging contaminants in sludge and wastewater
2019). Apart from these, secondary mechanisms such as sorption in the membrane and volatilization
have minor significance in the removal of ECs by MBR. However, EC removal can also happen by
retention in a second layer formed by particles retained in the membrane (Goswami etal., 2018).
Long SRT (>15 days) used in MBR promotes the enrichment of slowly growing microorganisms,
which improves the removal of ECs (Khan et al., 2020). Furthermore, other strategies can help
increase EC removal efficiency: (i) high HRT for longer EC retention and sorption improvement
(Liu et al., 2022); (ii) combination of diverse redox conditions (aerobic, anaerobic, and anoxic) to
enhance pollutant biodegradation (Dharupaneedi et al., 2019); and (iii) application of high-retention
membranes (i.e., forward osmosis and nanofiltration) to improve EC removal by size exclusion (Liu
et al., 2022).
7.2.1.3 Anaerobic digestion
The anaerobic digestion (AD) process involves a consortium of bacteria and archaea living in
syntrophism, applicable for both sludge and wastewater treatment (Figure 7.3b). Overall, organic
matter is enzymatically hydrolyzed by fermentative bacteria (hydrolysis step). Hydrolysis products go
through acidogenesis and acetogenic steps, generating less complex compounds. These compounds
are then converted to methane (CH4) and carbon dioxide (CO2) (Cremonez et al., 2021). Its application
depends on the characteristics of the wastewater and sludge, which directly influence the reactor
configuration. Wastewater treatment takes place in AD reactors such as the upflow anaerobic sludge
blanket reactor (USAB), and the anaerobic membrane bioreactor (AnMBR). Meanwhile, sludge
treatment occurs in digestors, a type of AD reactor normally applied to stabilize waste-activated
sludge from municipal WWTPs (Gonzalez-Gil etal., 2020; Oberoi etal., 2019). AD reactors require a
smaller installation area and can be employed in decentralized WWTPs to treat sludge and wastewater
generated in hospitals, industries, agriculture, and urban areas (Khan etal., 2020).
The affinity of AD for EC removal has been an object of study in the last few years. AD efficiency
for EC removal usually follows other biological processes’ tendencies toward lower efficiency because
of the molecular complexity and low biodegradability. Some ECs might negatively impact AD, reducing
the efficiency of organic matter removal and the generation of possible value-added products, such as
biogas production (Hube & Wu, 2021). However, its efficiency appears to be higher than that of other
processes, such as CAS and GAS. Therefore, ECs can be easily biodegraded or endured after AD. It is
suggested that reductive dehalogenation and cleavage of ether bond reactions are predominant, and
the presence of electron-withdrawing or electron-donating groups plays a role in the fate of ECs in AD
(Akpasi etal., 2023; Dubey eta l., 2021; Gonzalez-Gil eta l., 2020). This ease of biodegradability is shown
in the literature, where higher removal (∼80%) was found in ECs with ether bonds and electron-donating
groups in their molecules (e.g., acetaminophen, sulfamethoxazole, trimethoprim, and naproxen) when
compared to the removal (∼30%) of more complex molecules, such as those with esther and multiple
cyclic and multiple bonds (e.g., carbamazepine, diclofenac, ibuprofen, and terbutryn). It is important to
highlight that recalcitrant ECs and some TPs can remain sorbed in the sludge, which might negatively
affect the microbial community (Dubey etal., 2021; Gonzalez-Gil etal., 2020).
In summary, biodegradation of ECs by AD requires compatibility between their chemical structure
and the active site of the enzymes produced in one of the four steps of AD (Gonzalez-Gil etal., 2017).
Operational strategies to improve AD efficiency to remove ECs are: correct choice of inoculum source
to reduce the acclimatation period; careful acclimation period to allow the microbial community
adaptation to the sludge or wastewater characteristics; and adjustment of the operational parameters
(e.g., temperature, micro-aeration, pH, SRT, and organic loading rate) (Gonzalez-Salgado etal., 2020;
Nascimento etal., 2021; Panigrahi & Dubey, 2019; Vene gas etal., 2021).
7.2.1.4 Nitrogen removal
Nitrogen removal at WWTP is essential for environmental protection. CAS and GAS can partially
remove the nitrogen fraction from wastewater; however, highly concentrated streams require a
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120 Detection and Treatment of Emerging Contaminants in Wastewater
complementary treatment to meet treated wastewater standards. The conventional treatment for
nitrogen removal is the nitrification and denitrification process, which takes place under distinct
conditions. Nitrification converts ammonia into nitrate by the action of two autotrophic and aerobic
bacteria groups: ammonia-oxidizing bacteria and nitrite-oxidizing bacteria. Then, denitrification
occurs by converting nitrate into nitrogen through denitrifying bacteria, which requires heterotrophic
and anoxic conditions.
Both nitrification and denitrification contribute to EC removal through biodegradation and
adsorption mechanisms (Figure 7.2e, g, and h). However, mechanistic studies have focused on
understanding the role of nitrifying bacteria rather than the denitrifying group. EC removal during
nitrification has been associated with biodegradation via co-metabolism (James & Vijayanandan,
2023). Several studies suggest that the enzyme ammonium monooxygenase (AMO) acts as a catalyst
for EC biodegradation in the presence of ammonia (Alvarino etal., 2018). Nevertheless, AMO might
be selective for some ECs owing to its physicochemical properties (e.g., polarity, size, and functional
groups) and ability to diffuse across the cell membranes (Dawas-Massalha et al., 2014). Conversely,
the role of denitrification in EC removal still needs to be clarified. Some studies found no relevant
contribution from denitrifying bacteria on EC removal (Alvarino etal., 2018), while others observed a
correlation between denitrifying activity and antibiotic biodegradation (Langbehn eta l., 2021; Oberoi
etal., 2019).
Aside from bacterial activity, modifications in the nitrification and denitrification process could
also impact EC removal. Simultaneous nitrification and denitrification (SND) has been considered a
promising treatment for the simultaneous removal of nitrogen and EC (James & Vijayanandan, 2023).
SND has economic advantages over conventional nitrification and denitrification, requiring a small
implementation area and fewer carbon sources and oxygen inputs. In an SND system, nitrification and
denitrification occur in the same reactor, allowing the growth of a wide diversity of microorganisms,
developing different redox conditions, and, consequently, novel metabolic pathways for nitrogen
removal (James & Vijayanandan, 2023). Likewise, those modifications could influence EC removal
in SND (Liu etal., 2017; Sun etal., 2019). Nevertheless, further studies are necessary to understand
the removal mechanisms and evaluate if SND improves the EC removal efficiency compared to the
conventional nitrification and denitrification process.
7.2.2 Non-conventional
7.2.2.1 Constructed wetlands
Constructed wetlands (CW) is a wastewater treatment with low operating costs and energy input
(Xiong e t a l ., 2023). These syst ems are composed of water, substrate, microor ganisms, a nd plants, which
combine physical, chemical, and biological processes to remove organic and inorganic compounds
during secondary or tertiary treatment (Figure 7.3f). Different mechanisms, such as volatilization,
sorption, plant uptake, photodegradation, and biodegradation can co-occur. These mechanisms
can be identified according to the targeted EC through controlling operational conditions (e.g., pH,
temperature, HRT, batch or continuous operation mode, and plant species) (Gorito etal., 2017).
CWs can be configured by employing different locations for the water matrices and directions of
flow. Some configurations are surface flow, horizontal subsurface flow, and vertical subsurface flow
(Gorito etal., 2017), apart from specific configurations such as hydroponic gravel bed configuration
(allowing growth without soil) and restoration wetland (employing wastewater or WWTP discharges
as matrix). The EC removal in these systems is challenging to predict since multiple factors, such as
operational and environmental conditions, vegetation, EC chemical properties, and insolation, can
influence it (Verlicchi & Zambello, 2014).
According to Verlicchi and Zambello (2014), high removal percentages for multiple ECs were
observed in the literature, that is, acetaminophen, caffeine, ibuprofen, naproxen (>99%), and triclosan
(98%), in surface flow CW acting as a primary treatment. Venditti et al. (2022) observed a >90%
removal efficiency for 27 EC spiked (1–5 µg/ L) in synthetic wastewater in a vertical flow CW that
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121Treatment approaches for emerging contaminants in sludge and wastewater
operated for 357 days. CW enhances EC removal mechanisms because of its anoxic–aerobic–anaerobic
microregions; as a consequence, CW can remove a broad spectrum of EC.
Despite the good EC removal obtained by CW, more studies are needed to verify the feasibility and
applicability of WWTPs with optimized operational conditions to enhance the removal of critical
compounds. Looking at it from a more realistic point of view, CWs are suitable for small urban or rural
communities because of their low implementation and maintenance costs. Also, it could be utilized as
a polishing step in specific locations, such as hospital facilities (Verlicchi & Zambello, 2014).
7.2.2.2 Composting
Composting is a recognized method for managing organic waste, including sludge from WWTP. This
process involves the biological decomposition of organic matter under controlled conditions, resulting
in a safe soil amendment product (Congilosi & Aga, 2021).
In the context of ECs, composting can play a significant role in their reduction. The microbial
communities involved in composting can degrade various ECs, reducing their concentrations in the
final compost product (Iranzo et a l., 2018). However, the efficiency of this process can vary sig nificantly
depending on the nature of the contaminants and the composting conditions.
The composting process can also contribute to reducing ECs in the sludge. However, the fate of
these contaminants in the compost and the potential environmental and public health risks associated
with compost require further investigation (Kakimoto & Onoda, 2019).
As depicted in Figure 7.3d, the composting process involves several stages, each characterized by
different microbial activities and environmental conditions. T hese stages can influence the degradation
of ECs and the overall efficiency of composting (Xia etal., 2005).
Nonetheless, it is important to note that while composting can effectively reduce the concentration
of ECs in sludge, it may not completely eliminate all contaminants. Certain ECs may exhibit resistance
to degradation and persist in the compost. Therefore, further research is needed to enhance the
efficiency of the composting process and to understand the fate of ECs during composting. One of the
concerns regarding this residual EC concentration remains the further use of the composting product,
such as in agriculture, where the leftover concentration can lead to accumulation in soil and related
environments in the long term (Lillenberg etal., 2010).
In summary, composting is a valuable tool for managing sludge from WWTP. It can contribute
to the reduction of ECs and the production of a valuable soil amendment. Careful management of
the composting process is necessary to ensure the safe use of the resulting compost and to minimize
potential environmental and public health risks.
7.2.2.3 Microalgae-mediated processes
Microalgae-mediated processes are considered an alternative to treating wastewater contaminated
with EC because of their resistance to harsh environmental conditions, high biomass growth rate,
and capacity to adsorb amino and nitro groups (typically present in EC molecules). Treatment costs
can also be lower than for other biological processes since the wastewater can already present the
nutrients needed for growth and oxygen supply is not required (Gondi e t al., 2022; Rempel et al .,
2021). In this view, the application of microalgae-mediated processes to remove EC has been reported
as a circular economy strategy since CO2 is fixated during the process, generating a biomass that can
produce value-added products (Chhandama etal., 2023).
EC removal by microalgae can occur through five mechanisms: (i) bioadsorption, (ii)
bioaccumulation, (iii) biouptake, (iv) biodegradation, and (v) photodegradation (according to Figure
7.2a, b, d, and e). Briefly, (i) EC can be adsorbed into the algal cell wall or the EPS; (ii) it can bind
to the intracellular proteins in the non-living cell, and (iii) in the living cell; (iv) complex EC are
broken into simpler compounds, a process that is catalyzed by enzymes such as cytochrome P450 and
glutathione; if EC could not be bioremediated by the above, it can still be biotransformed through (v)
photodegradation, either by the EC reaction with oxidants (photooxidative degradation) or by the
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122 Detection and Treatment of Emerging Contaminants in Wastewater
absorption of light (photolysis) (Gondi et al., 2022). Over these five mechanisms, biodegradation is
reported as the main mechanism for EC removal. Ouada etal. (2019) observed that, while analyzing
diclofenac removal by Picocystis sp., bioadsorption and bioaccumulation contributed only 3.87%,
while biodegradation accounted for 69% of the removal efficiency.
Although the microalgal-mediated process presents some cost advantages, some challenges are
involved. Contamination with zooplankton and herbivorous protozoa in open tanks can reduce algal
biomass production by up to 90% (Gondi etal., 2022). Biomass harvesting after the treatment and its
downstream processing are key factors that hinder the scale-up since they account for 20–30% of the
total operational cost on the pilot scale. Also, further research about integrated approaches with other
treatments for removing EC from wastewater is necessary. More investigations are needed to evaluate
the actual applicability of microalgae in this context, such as optimized strains and operational
conditions that can maximize EC removal efficiency and biomass production (Gondi etal., 2022).
7.2.2.4 Mycoremediation
Mycoremediation uses fungi to mitigate the impact of pollutants on the environment. A fungus can
remove ECs from wastewater by different pathways. It can work as an adsorbent, a phase-transfer
process, adsorbing the molecule on its surface, and biotransforming using enzymes, as depicted in
Figure 7.2e, f, g, and h (Akpasi etal., 2023). Fungal metabolism works through enzyme production
with intra and extracellular mechanisms (Va ksmaa et al., 2023). In both ways, enzymes degrade
the compound into different and less harmful TP (Pereira etal., 2020). Among the fungi that can be
employed in EC degradation, the white-rot fungi are the most used, being the group responsible for
degrading lignin and allowing wood decomposition in nature (Gao etal., 2010).
Researchers demonstrated the Trametes versicolor potential to degrade some pesticides, reaching
100% malathion degradation (Hu et al., 2022). In enzymatic exploration, they showed that the
intracellular enzyme cytochrome P450 was substantially involved in the process. Aspergillus terreus
GS28 could adsorb/degrade 98% of azo dye from the sludge of the carpet industry within seven days,
showing its potential to decolorize textile wastewater (Hu etal., 2022). Moreover, Agrawal and Shahi
(2017) degraded 96.1% of the polycyclic aromatic hydrocarbon pyrene with Coriolopsis byrsina APC5
at pH 6 and 25°C.
Cruz-Morató et al. (2014) operated a 10-liter pilot-scale reactor filled with Trametes versicolor
pellets to assess the removal of pharmaceuticals and endocrine disruptors from non-sterile real
hospital wastewater. They obtained promising results in the degradation of antibiotics, with
removal percentages above 77%. Additionally, the process reached a removal efficiency of 80% and
100% for venlafaxine and diclofenac, respectively. However, other ECs remained resistant to the
mycoremediation. For instance, caffeine had a removal rate of 38%.
By combining adsorption, biotransformation, and low substrate specificity, mycoremediation
allows the degradation of a wide range of ECs (Va ksmaa etal ., 2023). However, its use on an industrial
scale is still challenging because of the slow growth of biomass, substrate competition with bacteria,
and the need for additional nutrients since wastewater does not provide enough for fungal growth.
Furthermore, mycoremediation requires longer HRTs that can last for days, and the fungal growth
should be as pellets or on carriers to avoid operational problems associated with fungal dispersion in
the liquid medium (Mir-Tutusaus etal., 2018).
7.2.2.5 Enzymatic processes
Enzymes are biocatalysts that can be employed to degrade a broad spectrum of ECs, such as dyes,
pesticides, and pharmaceuticals. Direct application of enzymes arose in the last few years as a way
to amplify the enzymatic activity that naturally occurs in other biological processes (e.g., CAS/GAS
and AD). Its sources are mainly bacteria and fungi (Rao etal., 2014). Within enzymatic processes,
oxireductases attracted interest because of the possibility of extracellular secretion, high biocatalyst
activity, operational flexibility, and lower substrate selectivity (Zdarta etal., 2018). A research review
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123Treatment approaches for emerging contaminants in sludge and wastewater
showed its potential to degrade various pharmaceutical compounds (e.g., non-steroidal hormones,
antibiotics, and anticancer drugs) (Pereira etal., 2020).
Studies showed that enzymes can biotransform hazardous substances into less harmful compounds,
mitigating their impact on human health and the environment (Ahsan eta l ., 2021; Pereira etal., 2023).
Tyrosinase from Agaricus sbisporus completely biotransformed phenol in an aqueous solution after 1 h
at 25°C (Shesterenko et al., 2012). Laccase from Myceliophthora thermophila could efficiently degrade
a mix of pharmaceuticals (anti-inflammatories and estrogen hormones) at trace concentrations within
less than 24 h (Lloret etal., 2010). Laccase from Trametes versicolor could also efficiently degrade the
anticancer drugs etoposide and doxorubicin into less harmful TP (Kelbert etal., 2021; Pereira etal.,
2023).
Although enzymes could perform reactions that even other catalysts could not achieve, their use
on a large or industrial scale can be tricky. Problems like enzymatic activity loss, biocatalyst reuse,
high enzyme cost, and low availability are the main drawbacks to the process’s scalability. Therefore,
researchers have worked on immobilization techniques to improve the enzymatic process and choose
the best support for each application (Daronch etal., 2020). Enzymatic immobilization allows its reuse,
increases enzymatic stability, and facilitates its separation from the final product, enabling its use on an
industrial scale to mitigate EC in wastewater (Zdarta etal., 2018). Despite several studies aiming to make
enzymatic processes feasible, the cost barrier has yet to be overcome; thus, this is not yet a widely applied
process. Thereby, even with decades of research, it can be considered an emerging technology for WWTP.
7.2.2.6 Bioelectrochemical systems
Bioelectrochemical systems (BES) are technological platforms based on the ability of some
microorganisms to generate an electrical current from the biodegradation of organic matter (Figure
7.3c). This electric current can be employed for several purposes, for example, power generation,
synthesis of value-added products, and remediation (Langbehn et al., 2021). The versatility of BES
includes the r eactor design (single, double, or multiple cha nnels), the process or bioprocess i ncorporated
in the system, and the electrode materials (carbon, metal, or modified).
The types of BES most explored for EC removal are microbial fuel cells (MFC) and microbial
electrolysis cells (MEC). Other BES arrangements have also been explored in the EC field, specifically
the MFC hybridization with other processes like CW, microalgae, and Fenton (Gupta et a l ., 2022; Sathe
etal., 2022). Sathe etal. (2022) analyzed the published literature about MFC coupled with Fenton
oxidation (MFC-Fenton) and its potential to remove ECs. This process has been demonstrated to be
effective for removing several ECs, for example, dyes, pesticides, pharmaceuticals, and heavy metals.
The degradation of most of the EC occurred very rapidly; however, the complete mineralization might
require a prolonged reaction time. Moreover, MFC-Fenton requires fewer chemicals and energy inputs
to degrade ECs than Fenton oxidation.
As in other bioprocesses aforementioned, biodegradation and adsorption are the main mechanisms
involved in EC removal. However, EC adsorption can occur in the biofilm or electrode material
(Gupta etal., 2022; Syed etal., 2021). Moreover, BES can exhibit different redox conditions that may
play a role in EC removal, improving its performance in contrast to other processes. The increase
in current with lower external resistance in MFC contributes to improving the removal efficiency of
conventional pollutants. However, the available literature indicates that the best MFC performance
to remove ECs might occur with external resistance values close to the MFC internal resistance
(Fernando etal., 2 014; Jiang etal., 2021).
In the context of WWTP, BES faces physical, energetic, and biological challenges to achieve
its commercial implementation (Gupta et al., 2022). Physical challenges comprise scalability and
capital costs. Electrodes and membranes commonly used in lab-scale BES are unaffordable for the
economic viability of large scale. Moreover, large-scale reactors rarely achieve treatment and energetic
efficiencies comparable to lab-scale ones. The energetic challenges include high internal resistance,
limited electrode conductivity, and sub-optimal contact between the electrodes.
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124 Detection and Treatment of Emerging Contaminants in Wastewater
In summary, BES shows promising results at a lab-scale level for simultaneous EC removal and
power generation. However, the mechanisms involved in EC removal, the behavior of mixed-culture
bioelectrodes, and the electron transfer mechanism still need to be well elucidated. Likewise, process
optimization regarding reactor design, electrode and membrane materials, and energy storage methods
is necessary for the large-scale application of BES.
7.3 PHYSICOCHEMICAL PROCESSES
The physicochemical processes for EC removal in sludge and wastewater are presented in this topic.
Some conventional and emergent technologies are discussed: advanced oxidation processes (AOPs),
adsorption, membrane filtration, and pyrolysis. ECs are converted chemically in AOPs and pyrolysis
technologies, while in adsorption and membrane filtration, there is only physical retention, moving
the contaminant to another matrix. Figure 7.4 summarizes the mechanisms involved in EC removal/
degradation by the physicochemical processes described in this topic.
The physicochemical processes studied for EC removal are generally used as a tertiary treatment
in WWTP after a biological treatment. Using these technologies as the primary treatment could
significantly increase operational costs. If AOPs were applied to raw wastewater, the free radicals
produced would attack not only ECs but all other substances present in the waste (Khan etal., 2020).
A pre-treatment should be employed to prevent scaling and fouling in membrane filtration processes,
reducing the frequency of cleaning cycles and membrane deterioration (Dharupaneedi etal., 2019). For
the adsorption process, saturation of the active sites will happen fast with a higher organic load in the
waste, reducing the life-cycle of columns and increasing process costs (regeneration and replacement
of the adsorbent). In contrast, the pyrolysis application is more common in sludge treatment and is an
effective option for ECs and other substance degradation.
7.3.1 Advanced oxidation processes
AOPs are a set of technologies designed to treat wastewater and sludge by generating highly reactive
radicals capable of degrading a w ide range of ECs. Overall, these processes are based on the production
of different types of free radicals that exert specific oxidation effects on the treated matrix, as depicted
in Figure 7.4a.
The most common methods include ozonation, Fenton’s process, photoprocesses, catalytic
processes, photocatalysis, electrochemical oxidation, persulfate technology, and plasma technology
(Oturan & Aaron, 2014; Wang et al., 2023). Each AOP has unique characteristics and operational
parameters that influence its effectiveness in treating wastewater and sludge. For instance, while
ozonation can degrade a wide range of ECs, it requires a high energy input and can produce harmful
by-products (Dubey etal., 2021). On the other hand, Fenton’s process is highly effective but can be
limited by the need for acidic conditions and sludge production (Gomes etal., 2017). Photocatalysis
and electrochemical oxidation are versatile and effective but have limitations, such as the need for
ultraviolet (UV) light and a power source, respectively (Lin et al., 2022; Oturan & Aaron, 2014).
Despite their effectiveness, the efficiency of AOPs can be influenced by various factors, including the
nature and concentration of the ECs, the presence of other substances in the wastewater or sludge,
and the operating conditions of the process (Ribeiro etal., 2019).
While AOPs can significantly reduce the concentration of ECs in wastewater and sludge, they
may not mineralize all contaminants. Certain ECs may resist degradation and persist in the treated
wastewater or sludge, as well as resistant TPs, posing potential risks to the environment and public
health (Wang etal., 2023). According to Lin eta l. (2022), the TPs generated via various pathways (e.g.,
hydroxylation, dehydrogenation, and ring-opening reactions) during AOPs may be more toxic than
the parent compounds. Therefore, while AOPs can significantly reduce the concentration of ECs in
wastewater and sludge, the potential formation of toxic TPs and the persistence of certain ECs in the
treated wastewater or sludge should be taken into consideration (Lin etal., 2022; Wang etal., 2023).
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125Treatment approaches for emerging contaminants in sludge and wastewater
Overall, AOPs offer a promising approach to treating wastewater and sludge-containing ECs.
However, further research is needed to optimize these processes, overcome their limitations, and
ensure their effective and sustainable application in real-world settings.
7.3.2 Adsorption
Adsor ption is a separation process that con sists of the acc umulation of the adsorbate onto the ads orbent
surface through physical and chemical interactions (Bonilla-Petriciolet et al., 2019; Rempel et a l.,
2021). The efficiency of this process depends on the adsorbent, adsorbate, and solution characteristics,
such as surface area, porosity, point of zero charge, chemical structure, pKa, solubility, temperature,
and pH. The most crucial choice is which adsorbent will be used since it impacts adsorption capacity
and overall treatment cost (Dotto & McKay, 2020).
There a re various t ypes of ads orbents, and t hey can be class ified as convent ional and unconvent ional.
Conventional adsorbents include activated carbon, zeolites, silica gel, and activated alumina. In
Figure 7.4 Physicochemical processes used to treat wastewater and sludge: (a) advanced oxidation processes,
(b)adsorption, (c) membrane filtration, and (d) pyrolysis.
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126 Detection and Treatment of Emerging Contaminants in Wastewater
contrast, examples of unconventional adsorbents are new materials from agro-industrial wastes and
other renewable sources developed mainly to reduce costs (Crini etal., 2019). The process can operate
in continuous or batch mode. The continuous process is applied to larger volumes with small physical
space in a fixed-bed column, while the batch process optimizes operational conditions (Patel, 2022).
One challenge in scaling up is increasing adsorption efficiency by developing new column designs that
are feasible for WWTPs (Dotto & McKay, 2020).
Adsorption occurs in three main steps: (i) external diffusion, (ii) intraparticle diffusion, and
(iii) surface reaction (Figure 7.4b). Usually, the third step is not the limiting step, so external or
intraparticle diffusion controls the total adsorption rate. Studies should be carried out to fully evaluate
the adsorption process, such as the effects of pH, kinetics, isotherms, thermodynamics, desorption,
and regeneration. In column studies, it should also include the breakthrough curve. Various authors
mention the relevance of matrix pH and the adsorbent point of zero charge in EC adsorption, mainly
for pharmaceutical compounds. The pH variation can influence pharmaceuticals’ functional groups’
protonation and promote changes in the superficial adsorbent charge (Quesada etal., 2019).
The adsorption process can be applied as a complementary treatment for removing EC, as it
presents high removal efficiencies and a broad spectrum of low-cost adsorbents from renewable
sources. However, persistent issues, such as the adsorbents’ lifespan, must be addressed to scale up
the process. The saturation of adsorbents and prior regeneration can be time- and money-consuming.
Also, few papers address the disposal of adsorbents that can no longer be regenerated, which generates
another EC-contaminated waste. When treating a complex matrix containing organic loads and other
substances, such as wastewater, competition between the organic and inorganic compounds could
impair the overall EC removal efficiency. In the literature, articles that perform EC adsorption in
synthetic water/wastewater are more common, which denotes an ‘unrealistic’ scenario (Quesada
et al., 2019). Considering these challenges, a careful study should verify the feasibility of applying
adsorption as a step in WWTP.
7.3.3 Membrane filtration
Membrane filtration is a physical treatment that uses synthetic membranes (semi-permeable or porous)
to remove pollutants. Membrane processes based on pressure-driven operation are classified according
to their pore size as microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis
(RO). ECs removal by membrane filtration in wastewater treatment has been widely investigated in
the last two decades (Coccia & Bontempi, 2023). The removal efficiency is dependent on interactions
between membrane properties (hydrophobicity, surface charge, pore size, and morphology) and EC
characteristics (hydrophobicity, pKa, size, and charge) (Dharupaneedi etal., 2019).
According to membrane type and contaminants, some removal mechanisms can be involved: size
exclusion, sorption, and electrostatic repulsion (Figure 7.4c) (Khanzada et al., 2020). Size or steric
exclusion is related to membrane pore size and ECs molecular weight. Sorption is significant only at
the beginning of porous membrane system operation and irrelevant after membrane sites’ saturation.
Most of the driven-pressure membranes used in WWTPs are polymeric, which presents a negatively
charged surface that rejects ECs with the same charge.
It is difficult to delineate a single rule for ECs removal by membrane processes since their removal
efficiencies depend on the wide range of compounds, their respective characteristics, and the diverse
operational conditions (Khanzada et al., 2020). However, a general tendency observed was cited by
Kim etal. (2018), with an increasing order of ECs removal efficiencies: MF < UF < NF < RO.
In MF and UF processes, EC removal occurs predominantly by sorption mechanisms because the
membrane pore size is larger than the overall pollutants’ molecular sizes (Khanzada etal., 2020). In
those cases, membrane treatment is ineffective in removing more polar and less hydrophobic ECs
(Kim etal., 2018). NF and RO systems are the most effective for ECs removal, reaching 70 to >90%
rejection for the majority of ECs mainly because of the size exclusion mechanism (Dharupaneedi etal.,
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127Treatment approaches for emerging contaminants in sludge and wastewater
2019). However, low removal efficiencies were observed for compounds with smaller molecular sizes,
opposite charges to the membrane, and elevated log KOW values (Khanzada etal., 2020). High energy
consumption is the more relevant disadvantage of these systems, increasing the final operational cost
of wastewater treatment.
Despite membrane technology efficacy, there is a gap in ECs removal evaluation in full-scale systems
with real wastewater and the presence of multiple compounds (Kim etal., 2018). It will be possible to
better define membrane filtration operational conditions for this additional purpose for ECs removal
only in this case (Kumar et al., 2023). Furthermore, using membrane technologies for ECs removal
does not eliminate the problem because contaminants remain in the concentrated stream and need to
be discarded appropriately.
7.3 . 4 P yr o l ys i s
Pyrolysis is a thermochemical reductive process that occurs at high temperatures (100–1300°C) and in
an oxygen-free atmosphere to transform the organic matter of biosolids into stable and low-molecular
substances. The main products of pyrolysis are (i) biochar, a carbon-rich solid that may also retain
several nutrients; (ii) syngas, containing mainly CO, CO2, CH4, and H2; and (iii) bio-oil, a dark and
viscous liquid mixture of organic compounds and water (Figure 7.4d) (Racek etal., 2020).
Pyrolysis can be applied to the sludge treatment from W WTP, and its potential to remove EC
sorbed on biosolids has been investigated in recent years. The main mechanisms involved in EC
removal during pyrolysis are volatilization, transformation into other compounds, and mineralization
(Buss, 2021). Ross et al. (2016) observed that ECs with higher vapor pressures tend to be removed
primarily through volatilization. Conversely, ECs with lower vapor pressures are exposed to pyrolytic
conditions for a longer time. This extended exposure allows ECs to undergo thermochemical
degradation, gradually breaking down into TP until mineralization.
So far, researchers have demonstrated that pyrolysis removes a broad variety of EC with removal
efficiencies greater than 95%. Buss (2021) reviewed the degradation conditions of several compounds
during the pyrolysis treatment of sludge. The author found strong evidence that an average temperature
of 500°C is enough to degrade several classes of EC in sewage sludge, for example, pharmaceuticals,
polycyclic aromatic hydrocarbons, hexachlorobenzenes, hormone-like substances, microplastics, and
dioxins. Moreover, those studies suggest an ideal residence time of 30–60 min for the degradation of
EC during pyrolysis. However, some EC may be completely removed from biosolids with a retention
time of 5 min (Ross et al., 2016). Besides the high removal efficiency and the short residence time,
another advantage of pyrolysis is that the oxygen-free atmosphere reduces the regeneration of dioxins
and polychlorinated biphenyls during the cooling of biochar when compared to other thermochemical
processes (Buss, 2021).
The main drawback to treating sludge by pyrolysis is its high energy consumption. The sludge
dewatering step is essential for pyrolysis and has high energy consumption. This energy consumption
can be up to five times higher than the pyrolysis itself and needs an external energy supply, turning
the energy balance negative.
As mentioned before, a fraction of EC and its metabolites may only be shifted to the vapor phase;
therefore, a post-treatment of syngas is necessary to remove the volatilized fraction of EC and conclude
the degradation. However, this post-treatment may occur in the postcombustors installed in commercial
pyrolysis units to oxidize gaseous emissions generated during the sludge treatment (Buss, 2021).
7.4 TREATMENT TRENDS FOR ECS REMOVAL
Conventional WWTP rarely reaches complete EC removal, and, as a result, residual EC and TP are still
present in the treated wastewater and sludge. As discussed in Sect ion s 7. 2 and 7. 3 , no single technology
can effectively remove and/or degrade all ECs found in wastewater and sludge. Nevertheless, the
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128 Detection and Treatment of Emerging Contaminants in Wastewater
available literature points out perspectives and trends to enhance EC removal efficiencies with these
technologies.
Conventional biological processes in WWTPs could improve EC removal by increasing EC
biodegradation. This feature can be reached with the following strategies:
(a) Combining different redox environments: prioritize processes that allow the coexistence of
aerobic, anaerobic, and anoxic conditions, like GAS and SND.
(b) Operating parameter optimization: SRT strongly correlates with increased EC biodegradation.
(c) Waste pre-treatment: include a pre-treatment step, for example, hydrothermal, has been
demonstrated to enhance EC biodegradation in AD (Díaz etal., 2020).
(d) Employing additives: iron-based additives can regulate reaction conditions, electron transfer
mode, and microbial function in AD (He etal., 2022).
Some non-conventional bioprocesses have shown huge potential to improve EC removal and can
be considered a trend for W WTP. Enzymatic processes show high EC efficiency removal; however,
immobilizing enzymes on appropriate supports is critical to their use in WWTP. Therefore, creating
supports and developing reactors that offer more stability and allow effective enzyme reuse is crucial.
BES has also stood out due to its ability to remove EC while generating in-situ energy and other value-
added products. Moreover, the BES concept can be applied to bioprocesses (e.g., AD, CW, and nitrogen
removal) to amend microbial communities and enhance their efficiency. However, both technologies
need further studies to understand EC removal in actual scenarios, that is, multiple EC removal, real
wastewater, and scale-up.
The application of physicochemical processes to remove EC in WWTP can be favored by developing
new and advanced materials, for example, catalyzers, adsorbents, and membranes. Membranes stand
out for their versatility in WWTP, being applied in physicochemical and biological treatments. They
contribute to EC removal by size-exclusion mechanisms and also reduce the area required for the
treatment. Trends in membrane development are focused on increasing membrane rejection and
lifespan. Studies suggest that using high-retention membranes and developing advanced membranes
with mixed-based matrices and active layer functionalization enhance membrane rejection (Coccia
& Bontempi, 2023; Dharupaneedi et al., 2019; Khanzada etal., 2020). Meanwhile, forward osmosis
and membrane distillation have the potential to reduce membrane fouling and increase EC removal
(Goswami etal., 2018).
Despite all the previously mentioned strategies to improve EC removal in each process, there is a
consensus that a single technology will not solve the problem of EC in WWTP, and the best approach
would be to combine different processes (Besha et al., 2017; Langbehn etal., 2021). This approach
enables the application of complementary removal mechanisms (e.g., sorption, biodegradation,
chemical oxidation, and size exclusion) to remove and mineralize EC and improve the final effluent
quality. Recently, promising results were obtained with the following configurations: biological
treatment + membrane filtration (NF or RO) (Besha et a l., 2017); MBR + AOPs (Liu e t al., 2022);
AOPs + adsorption (Kumar etal., 2023); anaerobic–anoxic–oxic systems (AAO) (Ashfaq etal., 2 017);
and A2/O-MBR + UV/chlorine (Ren etal., 2022).
In summary, several processes can potentially mitigate EC contamination in wastewater and sludge,
and the removal efficiency is enhanced with optimized configurations, operational conditions, and
advanced materials. Nevertheless, it is worth noting that most of the studies published so far explore
the removal of pollutants in lab-scale and ideal conditions (i.e., one or similar ECs and synthetic
wastewater). While these studies provide insight into the fundamentals of removing EC, their findings
cannot be applied to real-life scenarios, which are far more complex than those simulated in these
studies. Therefore, it is also necessary to encourage further research to understand EC removal in
real-life scenarios to advance this topic.
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129Treatment approaches for emerging contaminants in sludge and wastewater
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© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0135
Lamia Yakkou1, Sofia Houida2*, Maryam Chelkha1, Imane Sarroukh3, Sartaj Ahmad Bhat4,
Rabha Abdelwahd5, Mohammed Ibriz3, Mohammed Raouane1, Souad Amghar1 and
AbdellatifEl Harti1
1Laboratoire LBVRN, Faculté des Sciences d’Agadir, Université Ibn Zohr, BP 8106, 8000 0, Agadir, Morocco/Faculty of Applied
Sciences- Ait Melloul, University Ibn Zohr, BP 8106, 80000, Agadir, Morocco
2Pasteur Institute of Morocco, Casablanca, Morocco
3Laborator y of Biolog y, nutrition, health and environment, Department of Biology, Faculty of Science, Ibn Tofail University, B.P. 133,
Kenitra 14000, Morocco
4River Basin Research Center, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan
5Biotechnology Research Unit, Institut National de la Recherche Agronomique (INRA), B.P. 415, Rabat, Morocco
*Corresponding author: sofia.houida@pasteur.ma
ABSTRACT
Emerging contaminants (ECs) such as pharmaceuticals, personal care products, and industrial chemicals pose an
increasing threat to both the environment and human health, with their presence being detected more frequently
in wastewater treatment plants and sludge. In response, fungal-mediated processes have emerged as a promising
bioremediation technology, offering the unique abilit y to degrade a wide range of pollutants present in sludge.
This chapter delves into the fungal species utilized for this purpose and recent advances in fungal-mediated
processes, including genetically modified and immobilized fungi and combinations with other treatment methods.
Furthermore, the mechanisms by which fungi remove ECs from sludge, such as biosorption, biodegradation, and
enzyme production, are comprehensively discussed. Factors affecting the efficiency of fungal-mediated processes,
including pH, temperature, fungal species, nutrient availability, and reactor design, are also examined. Finally, the
chapter outlines the challenges encountered when using fungal-mediated processes to remove ECs from sludge
and potential real-world applications of these processes in wastewater treatment scenarios.
Keywords: biodegradation, bioremediation, biosorption, emerging contaminants, fungal-mediated processes, sludge
8.1 INTRODUCTION
Sludge is a by-product generated while treating industrial wastewater combined with domestic swag
at an industrial facility, often containing various organic and inorganic contaminants that can pose
risks to human health and the environment (Turovskiy & Mathai, 2006). Traditional sludge treatment
Chapter 8
Novel approaches for removing
emerging contaminants from sludge
using fungal-mediated processes
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136 Detection and Treatment of Emerging Contaminants in Wastewater
methods may not effectively remove these emerging contaminants (ECs), leading to their persistence
in the environment (Vicent etal., 2013).
Many fungal species have gained significant attention in recent years for their potential to remove
ECs from sludge (Va ksmaa et al., 2023). Using fungi to remediate emerging pollutants has many
advantages over other physical and chemical mechanisms, such as its high effectiveness, low cost,
and environmentally friendly nature (Tomasini & León-Santiesteban, 2019). In addition, fungus
bioremediation has advantages over bacteria due to the diversity of processes, degrading enzymatic
capacities, and ability to function under broad pH conditions (Tomasini & León-Santiesteban, 2019;
Wani etal., 2017).
Through their mycelium, which is a network of filaments, fungi can absorb the ECs that are
present in the sludge. Hence, the contaminants may adhere to the mycelium’s surface or penetrate
the interior of the cells. The concentration of contaminants is then reduced as a result of this sorption
and absorption (Malik et al., 2023). Certain fungi use specific metabolic pathways to convert ECs
into less toxic molecules. These metabolites may be more easily degraded or less persistent in the
environment, aiding in the decontamination of waterways (Maqsood etal., 2023). Some mushrooms
can form complexes with ECs. These complexes may alter the contaminants’ solubility or reactivity,
making subsequent processes like precipitation or filtration easier to eliminate (Maqsood etal., 2023).
Furthermore, fungi develop symbiotic relationships with other microorganisms like bacteria. By
fostering interactions between various organisms, these may promote the degradation of ECs and
increase the overall effectiveness of the bioremediation process (Nguyen etal., 2013).
Novel approaches to removing ECs from sludge by fungal-mediated processes have been the
subject of active research. Some notable strategies and techniques have been investigated, including
co-cultivation of fungi, fungal bioaugmentation, genetic modification of fungi, fungal-assisted
phytoextraction, and fungal-based nanomaterials (Malik etal., 2022).
Nevertheless, these novel approaches’ effectiveness and practical applicability may vary depending
on the specific contaminants, fungal species, and environmental conditions. Further research and
development are needed to optimize these techniques and evaluate their scalability for large-scale
sludge treatment (Marshall etal., 2020).
In this chapter, we delve into the fungal species utilized for this purpose and recent advances in
fungal-mediated processes, including genetically modified and immobilized fungi and combinations
with other treatment methods. Furthermore, we highlight the mechanisms by which fungi remove
ECs from sludge, such as biosorption, biodegradation, and enzyme production are comprehensively
discussed. In addition, the factors affecting the efficiency of fungal-mediated processes, including pH,
temperature, fungal species, nutrient availability, and reactor design, are also examined. Finally, the
chapter outlines the challenges encountered when using fungal-mediated processes to remove ECs from
sludge and the potential real-world applications of these processes in wastewater treatment scenarios.
8.2 FUNGAL SPECIES USED FOR THE REMOVAL OF ECS
8.2.1 Fungal species used for the removal of ECs from sludge
Several fungal species have been studied and employed to remove ECs from sludge. Here we present
some commonly investigated fungal species in this context (Table 8.1). As shown in Table 8.1, the most
commonly used fungi species for removing ECs are Trametes versicolor and Pleurotus ostreatus. T.
versicolor is a white-rot fungus known for its versatile enzymatic system, which allows it to degrade
a wide range of organic compounds, including ECs like pharmaceuticals and personal care products.
It also exhibits metal-binding properties, making it helpful in removing heavy metals from sludge.
T. versicolor removed >99.9% and 40% of diclofenac and ketoprofen, respectively, within 14 days
(Dalecka etal., 2020). Another study using T. versicolor for diclofenac degradation reported >87%
removal in just 14 days (Hu etal., 2020). T. versicolor has also demonstrated its ability to break down
certain pesticides, including malathion and chlorpyrifos, by using enzymes such as peroxydase and
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137Novel approaches for removing emerging contaminants from sludge
Table 8.1 Fungal species used in ECs removal.
Species Emerging
Contaminant
Implicated
Enzymes
Duration of
Degradation
Removal
Efficiency (%)
References
Aspergillus sydowii Chlorpyrifos
Methyl parathion
Profenofos
Phosphoesterase
Methylesterase
10 days 32–80 Soares etal. (2021)
Bjerkandera adjusta Atrazine Cytochrome P450 — 92 Dhiman etal. (2020)
Ganoderma lucidum Diuron Laccase 15 days >50 da Coelho-Moreira etal. (2018)
Phanerochaete chysosporium Sulfamethoxazole Laccase 10 days 74 Guo etal. (2014)
Pleurotus ostreatus Diclofenac
Ketoprofen
Laccase 5 days 100
70
Palli etal. (2017)
Pleurotus ostreatus Atenolol Laccase 20 days 60 Palli etal. (2017 )
Pleurotus ostreatus Carbamazepine Cytochrome P450 7 days 68 Buchicchio etal. (2016)
Trametes versicolor Chlorpyrifos Laccase 7–14 day s 94.7 Hu etal. (2020)
Trametes versicolor Gemfibrozil — 30 days 77–82 Alamo etal. (2021)
Trametes versicolor Hydrochlorothiazide — 30 days 80–95 del Álamo etal. (2018)
Trametes versicolor Diazepam Laccase 15 days 66 Badia-Fabregat etal. (2016)
Trametes versicolor Bisphenol
Nonylphenol
Parabens
Phthalates
Laccase 2–7 days 45–60 Pezzella etal. (2017)
Trametes versicolor 17α-ethinyl-estradiol Laccase 24 hours 83 Becker etal. (2016)
Trametes versicolor Carbamazepine
Trimethoprim
—14 days 88.6–89.8 Tormo-Budowski etal. (2021)
(Continued)
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138 Detection and Treatment of Emerging Contaminants in Wastewater
Table 8.1 Fungal species used in ECs removal (Continued).
Species Emerging
Contaminant
Implicated
Enzymes
Duration of
Degradation
Removal
Efficiency (%)
References
Trametes versicolor Sulfamethoxazole Laccase 48 hours 34–82 Alharbi etal. (2019)
Trametes versicolor Diclofenac Laccase 2–7 days 39–95 Stenholm etal. (2019)
Trametes versicolor Dicofol —14 87. 9 Hu etal . (2020)
Trametes versicolor Cypermethrin —14 93.1 Hu etal. (2020)
Trametes versicolor Diuron
Bentazon
Laccase 27 days 93 Beltrán-Flores etal. (20 21)
Trametes versicolor Sulfamethoxazole del Álamo etal. (2018)
Trametes versicolor Ibuprofen
Ketoprofen
Naproxen
Laccase 49 days 60–90 Torán etal . (2017)
Trametes versicolor Bezafibrate
Gemfibrozil
Ketoprofen
Ibuprofen
Naproxen
Laccase 14 –21 days >80 Mir-Tutusaus etal. (2018)
Trichoderma pubescens Amoxicillin — 24 hours 98 Cai etal. (2023)
Badia-Fabregat etal. (2016)
T. versicolor Diclofenac
Ketoprofen
—14 days >99.9
40
Dalecka etal. (2020)
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139Novel approaches for removing emerging contaminants from sludge
laccase (Ma & Ruan, 2015). The ability of T. versicolor to use peroxydases and other enzymes to
break down polycyclic aromatic hydrocarbons (PAHs), including naphtalene and pyrene, has also
been investigated (Baldrian etal., 2000).
Another edible mushroom species, P. ostreatus, has been studied for its ability to degrade organic
pollutants, such as PAHs and textile dyes, in sludge. P. ostreatus has a high capacity for lignin
degradation and can break down complex organic compounds (Purnomo et al., 2010). P. ostreatus
has proven its capacity to effectively decolorize and break down a variety of synthetic dyes, including
azoic and triphenylmethane dyes, by using its ligninolytic enzymes (peroxydases and laccases) (Levin
etal., 2004). Additionally, P. ostreatus has been studied for its capacity to degrade organic pollutants,
such as pesticides and herbicides, in contaminated soil and water (Purnomo etal., 2010). P. ostreatus
may also degrade PAHs found in soil and sediments, assisting in the degradation of these pollutants
(Pozdnyakova etal., 2018).
Known as a potent white-rot fungus, Phanerochaete chrysosporium has been extensively studied
for its ability to degrade recalcitrant organic pollutants, including pesticides, herbicides, and industrial
chemicals. Its unique enzymatic system allows it to break down complex organic compounds and
transform them into more straightforward, less harmful forms. Aspergillus niger is a filamentous
fungus with a robust enzymatic system capable of degrading various organic compounds. It has also
been investigated for its potential to remove pharmaceuticals and other organic pollutants from sludge
(Arun etal., 2023).
The filamentous fungal species of Aspergillus has been reported to be able to degrade PAHs,
chlorophenols, and aliphatic hydrocarbons (Malik et al., 2022). A. niger can produce extracellular
enzymes, such as ligninases and cellulases, which aid in the break down of complex organic molecules.
Moreover, several species of Penicillium, including Penicillium chrysogenum and Penicillium
purpurogenum, have shown promise in removing ECs from sludge. These fungi possess diverse
enzymatic capabilities and can degrade various organic compounds, including pharmaceuticals and
industrial pollutants (Leitão, 2009).
It is important to note that selecting a specific fungal species for sludge remediation depends on the
targeted contaminants and environmental conditions (Somu etal., 2022). Different fungi may exhibit
varying degrees of efficiency and substrate specificity. Additionally, research is ongoing to explore the
potential of other fungal species and optimize their performance to remove ECs from sludge (Rafeeq
etal., 2023).
The primary agents of ligninous material biodegradation in nature are white-rot fungi (WRF).
The majority of studies have shown that WRF, such as P. chysosporium, T. versicolor, Bjerkandera
adjusta, and Pleurotus sp., can bioremediate through the production of various ligninolytic enzymes
like laccases and peroxidases. T. versicolor (García-Galán et al., 2011; Rodríguez-Rodríguez et al.,
2012b), P. chrysosporium (Huang etal., 2017), and Phlebia tremellosa (Kum etal., 2011) are some of
the most common WRF when it comes to bioremediation of contaminants (Marco-Urrea et al., 2010;
Rodríguez-Rodríguez et al., 2010). A similar role has also been reported for Penicillium spp. (Li etal .,
2020). Other examples of pollutants are anthracene, which is removed by the fungi Irpexlacteus and
P. ostreatus (Drevinskas et al., 2016); pyrene by Ganoderma lucidum (Agrawal et al., 2018); and
chrysene by Polyporus spp. (Hadibarata et al ., 2009). These fungal groups have also been able to
degrade toxic metals with high bioremediation efficiency. For example, P. ostreatus (white-rot fungus)
is known to aid in bioremediation by degradation of crude oil and toxic metals, with bioremediation
efficiency within the range of 28.2–75.9% (Anacletus etal., 2 017).
8.2.2 Mechanisms by which fungi can remove ECs from sludge
Fungal species offer several advantages for the remediation of sludge contaminated with ECs. Firstly,
fungi can degrade a wide range of organic compounds due to their diverse enzymatic systems. This
versatility allows them to break down complex organic pollutants, including pharmaceuticals,
personal care products, pesticides, and industrial chemicals present in sludge (Rodríguez-Rodríguez
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140 Detection and Treatment of Emerging Contaminants in Wastewater
et al., 2013). Moreover, some fungal species have the capability to transform or bind with heavy
metals and metalloids, thereby reducing their toxicity and mobility. This is particularly beneficial
when sludge contains elevated levels of heavy metals, such as lead, mercury, or arsenic, which can
harm ecosystems and human health (Abd Elnabi etal ., 2023; Priyadarshini et a l ., 2021). In addition to
their degradation and binding capacities, fungi can also assist in the removal of nutrients from sludge.
Excessive levels of nutrients, such as nitrogen and phosphorus, can contribute to eutrophication when
sludge is applied as fertilizer. Certain fungal species, like WRF, can efficiently break down organic
forms of nitrogen and phosphorus, reducing their availability and minimizing the risk of nutrient
pollution (Bhambri et al., 2021). While fungal species used for sludge remediation show promise,
further research and development are needed to fully understand their potential, optimize their
performance, and scale up their application in practical wastewater treatment systems. Nevertheless,
using fungal species holds excellent potential for removing ECs from sludge, offering a sustainable
and environmentally friendly approach to sludge management (Aydin, 2016; Rodríguez-Rodríguez
etal., 2013).
Fungi can employ various mechanisms to remove ECs from sludge. Here are some key mechanisms
by which fungi contribute to the degradation, transformation, or sequestration of contaminants
(Figure 8.1):
Enzymatic degradation: One of the key characteristics of fungi involved in the elimination of ECs is
their production of specific enzymes. Fungi possess a diverse array of enzymes that play a crucial role
in the degradation of organic contaminants. Extracellular specialized enzymes that can degrade ECs
include the peroxydases, hydrolase, oxidoreductase, dehalogenase, oxygenase, transferase, laccases,
and ligninases, which have the ability to break down a wide range of chemical compounds, including
recalcitrant pollutants like PAHs and pharmaceuticals (Kothawale etal., 2023; Levin et al., 2004;
Naghdi etal., 2018).
Pozdnyakova et al. (2018) investigated the biodegradation potential of the PAH compounds,
phenanthrene and anthracene using the fungi Agaricus bisporus and P. ostreatus (Pozdnyakova etal.,
2018). Evidence showed that the laccases produced by A. bisporus turned the PAH compounds into
their quinone analogues. On the other hand, P. ostreatus has also evolved flexible peroxidase enzymes.
Figure 8.1 Various mechanisms employed by fungi to remove ECs.
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141Novel approaches for removing emerging contaminants from sludge
On another study, the HPLC analysis of fungal metabolites confirmed that a novel strain of the fungus
Coriolopsis byrsina could split the aromatic rings of pyrene and degrade it into pyrene trans-4,5-
dihydrodiol by producing laccase enzymes. In addition, manganese peroxidase converted anthracene,
phenanthrene, pyrene, and fluoranthene into quinones by demineralization and oxidation (Baborová
et al., 2006). In the field of environmental biotechnology, these discoveries hold great potential for
the remediation of PAH-contaminated sites. Understanding the enzymatic degradation of PAH by
fungi can pave the way for developing sustainable and eco-friendly solutions to tackle the persistent
problem of polycyclic aromatic hydrocarbon pollution.
The emergence of exogenous redox mediators, which act as transport molecules in the process, may
aid in degradation. Azoreductase is a flavodoxin protein that breaks the azo bonds in dyes. This made
it possible for the dyes to be changed into the right aromatic acids (Maqsood etal., 2023).
Furthermore, laccases were found to be involved in the break down processes of dicofol and
chlorpyrifos in T. versicolor (Table 8.1). The first step is dechlorination, which converts dicofol to
2,2-dichloro-1,1-bis(4-chlorophenyl)-ethanol. These oxidative cleavages and dechlorinations result in
4,4′-dichlorobenzophenone. Benzaldehyde is made when enzymes that break down lignin break the
ring structure of lignin (Purnomo etal., 2010).
Recently, more and more studies have shown that the enzyme cytochrome P450 is involved in
removing and breaking down organic pollutants. The CYP450s are a diverse superfamily of enzymes
with specialized folding properties. The hydroxylation, N-, O-, S-dealkylation, sulfurization,
epoxidation, deamination, desulfurization, dehalogenation, peroxidation, and N-oxide reduction
reactions are just a few examples of the various reactions that these enzymes, which are either located
in the cell membrane or the cytoplasm, contribute to the transport, metabolism, and catabolism of
organic substrates (Roccatano, 2015). In order to oxidize an inert substrate, for instance, CYP450
first breaks the strong bond between C and H before creating a stronger bond between O and H
(Dacco et al., 2020). Therefore, CYP450s can catalyze ECs of various sizes and shapes (Deshmukh
etal.,2016).
Co-metabolism: Fungi can utilize contaminants as co-substrates or co-metabolites for their
metabolic processes. In some cases, fungi may not fully mineralize the contaminants but transform
them into less toxic or less persistent metabolites. This co -metabolic activit y can lead to the degradation
or detoxification of ECs in sludge (Deshmukh etal., 2016).
Adsorption and sequestration: Fungi can bind or adsorb contaminants onto their cell walls or
extracellular matrices. The fungal cell wall is composed of polysaccharides, proteins, and other
biomolecules that can act as sorbents for various contaminants. This adsorption mechanism can lead
to the immobilization or sequestration of contaminants, reducing their bioavailability and potential
for environmental impact (Crini etal., 2018).
Metal complexation and binding: Some fungi can sequester and bind heavy metals in sludge.
They can produce metal-binding molecules, such as organic acids, peptides, and extracellular
polymeric substances that form complexes with metal ions. This metal complexation can reduce
the mobility and bioavailability of heavy metals, mitigating their potential toxic effects (Qian
etal.,2017).
Mycelial uptake and accumulation: Fungal mycelium, consisting of interconnected branching
hyphae, can act as a physical network for the uptake and accumulation of contaminants. Mycelium
can penetrate through sludge particles, creating a vast surface area for contact with contaminants.
Fungi can absorb contaminants into their mycelium, effectively concentrating and sequestering them
within their biomass (Qian etal., 2017).
Synergistic interactions: Fungi can establish synergistic interactions with other microorganisms,
such as bacteria, to enhance contaminant removal. Some bacteria can produce enzymes or metabolites
that complement the degradation capabilities of fungi. Co-cultivation or biofilm formation involving
fungi and bacteria can create a cooperative network that leads to improved degradation efficiency
(Angeles-de Paz etal., 2023; Espinosa-Ortiz etal., 2022; Purnomo etal., 2020).
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142 Detection and Treatment of Emerging Contaminants in Wastewater
It is important to note that the mechanisms fungi employ for contaminant removal can vary
depending on the specific fungal species, contaminants present, environmental conditions, and the
interplay with other microorganisms (Kumar etal., 2021).
8.3 RECENT ADVANCES IN FUNGAL-MEDIATED PROCESSES FOR EC REMOVAL
Recent years have witnessed significant advances in fungal-mediated processes for the removal of ECs
(Figure 8.2). Moreover, as mentioned in the previous section of this chapter, a considerable research
effort on fungi capacities demonstrates that their biochemical and physiological characteristics can
be necessary for a wide range of biotechnological applications to be used for degrading organic
contaminants. As a result of their great promise, this chapter highlights recent advances and novel
approaches for using these microorganisms to remove ECs.
Figure 8.2 Papers related to the new technologies using fungi to remove ECs (the graph was created using
Connected Papers website).
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143Novel approaches for removing emerging contaminants from sludge
Researchers have been exploring the fungi’s enzymatic systems and metabolic pathways to better
understand their potential for EC removal. Studies have focused on identifying novel enzymes involved
in degrading specific contaminants and optimizing their activity. Additionally, transcriptomic and
proteomic analyses have provided insights into fungi’s gene expression and protein profiles during
the degradation process (Malik etal., 2022). Furthermore, the advances in genomic and metagenomic
studies have facilitated the discovery and characterization of fungal species and their functional
genes involved in EC degradation. High-throughput sequencing technologies have made it possible
to identify different fungal communities in sludge and assess their potential for pollutant removal.
Metagenomic approaches have also shed light on fungal populations’ genetic diversity and metabolic
potential in sludge ecosystems (Bala etal., 2022).
The application of molecular tools, such as quantitative polymerase chain reaction (qPCR) and high-
throughput sequencing, has facilitated the monitoring and assessment of fungal-mediated processes.
These tools allow for quantifying fungal populations, tracking the expression of key genes involved
in degradation, and assessing changes in fungal community structure and dynamics during the
remediation process (Akerman-Sanchez & Rojas-Jimenez, 2021; Kour etal., 2021; Somu etal., 2022).
These recent advances demonstrate the growing understanding of fungal-mediated processes for EC
removal and highlight the potential for more efficient and targeted strategies. Continued research
and technological development in this field hold promise for the implementation of sustainable and
effective fungal-based approaches to sludge remediation (Kour etal., 2021).
8.3.1 Fungal reactors
The development of bioreactor systems for fungal-mediated contaminant removal has gained
attention. Bioreactors provide controlled environments that optimize fungal growth and activity for
efficient degradation. Various configurations, such as submerged, solid-state, and biofilm reactors,
have been explored to enhance fungal performance in sludge treatment. Integration of bioreactors
with advanced monitoring and control systems allows for real-time optimization of process conditions
(Tormo-Budowski etal., 2021).
In contrast to ex situ bioremediation techniques, using a bioreactor to treat emerging pollutants
has a number of advantages as of late. The time needed for bioremediation can be greatly decreased
by using an effective bioremediation process based on bioreactors that can precisely control pH,
agitation, temperature, aeration, substrate concentration, and inoculum concentration. When the
bioreactor can be managed and controlled, biological reactions can occur. Bioreactor designs are
flexible enough to maximize microbial degradation while minimizing abiotic losses (Bala etal ., 2022).
They are therefore a viable option for cleaning contaminated areas. To get rid of various classes of
emerging pollutants, a biotechnological method that used the fungus T. versicolor in a sludge-bioslurry
reactor was evaluated. For 24 pharmaceuticals that were detected but either removed or completely
degraded, this technique demonstrated efficiencies over 50% (Rodríguez-Rodríguez etal., 2012a).
In a membrane bioreactor supplemented with the fungus T. versicolor and activated sludge, Nguyen
e t al . (2013)’s research examined the brea k down of 30 trace organic pollutants in synthetic wastewater.
In comparison to a typical membrane bioreactor containing simply activated sludge, the fungus,
along with bacterial strains, had a better removal rate of trace organic pollutants (80%). Moreover,
the fungus-bacteria enhanced bioreactor eliminated fenoprop, clofibric acid, pentachlorophenol,
ketoprofen, diclofenac, and naproxen (Pathak etal., 2020). In these experiments, the synergistic break
down by the bacteria and fungus was attributed to the improved elimination of organic pollutants. In
fact, recent research indicates that using more than one living organism can increase bioremediation’s
effectiveness and results while allowing for a wider variety of microorganisms.
8.3.2 Coculture-based approach
Researchers have started investigating the potential synergistic interactions between fungi and
bacteria for enhanced contaminant removal. Fungi can provide a conducive environment for
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144 Detection and Treatment of Emerging Contaminants in Wastewater
bacterial growth, while bacteria can assist in the break down of complex contaminants and provide
additional enzymatic activities. Co-cultivation or biofilm formation involving fungi and bacteria has
shown promise in improving degradation efficiency (Espinosa-Ortiz etal., 2022). In fact, a microbial
consortia’s individual species interact with one another, which results in the development of various
traits like stability and the specialization of microbial partners to carry out particular functions
like degradation (Feng et al., 2019). However, it is challenging to isolate a sustainable microbial
combination that could be effective on a large scale (Gupta etal., 2022).
A published paper recently proposed an innovative method for creating a multi-domain co-culture
that can degrade many medicinal chemicals at once. In order to improve their degrading performance,
seven previously isolated microorganisms (fungi and bacteria) from sewage sludge were examined.
The strains were factorially combined, and they were then utilized to put together several artificial
co-cultures. The most effective co-cultures were tested with three distinct pharmaceutical substances
to gauge the rate of break down of developing pollutants. The minimum active microbial consortia,
which included co-existing bacteria as well as Cladosporium cladosporoides and Penicillium spp.,
had the best performance (>80% destruction). It was emphasized that these consortiums converted
the pharmaceutical active chemicals by hydroxylation. Therefore, high-throughput detection of
co-cultures can be a fast, reliable, and efficient method to reduce co-cultures’ degradation suitable for
ECs and avoid toxic by-products. However, the fact that microbial consortia are highly stable in vitro
does not ensure that in situ efficiency might not be negatively affected by external factors (Angeles-de
Paz etal., 2023). On the other hand, a socially stable consortium with significant degrading capacity
should be identified in order to assure the effective implementation of the artificial co-culture
construction, and more research is required to understand how it competes with native microbiota.
Thus, future metatranscriptomics and metaproteomics investigations will help in understanding the
processes of adaptability and the stability over generations of these artificial consortia (Angeles-de
Paz etal., 2023).
Figure 8.3 Articles related to the use of fungal–bacterial co-cultures to remove ECs (the graph was created using
Connected Papers website).
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145Novel approaches for removing emerging contaminants from sludge
Mixed microbial communities have distinctive interactions that can lead to more effective systems
for separating and removing organic contaminants. Adopting polymicrobial culture methods has
made it possible to get a deeper knowledge of microbial dynamics in mixed microbial communities of
fungus and bacteria. Compared to pure cultures of either fungus or bacteria, prior studies have found
that combining fungal–bacterial treatments results in greater biodegradation of certain contaminants
(Espinosa-Ortiz etal., 2022). The interaction of bacterial and fungal systems may result in synergistic
partnerships that can speed up the break down of organic contaminants. Graphic 1 summarizes the
most recent publications in the literature that used a variety of fungal–bacterial co-cultures to remove
organic contaminants.
When bacteria and fungi are co-cultivated, the production of enzymes can increase, helping to
fully mineralize contaminants, or secondary metabolites can be produced, which can help with
pollutant break down. In co-cultures, interactions that are either synergistic or antagonistic can lead
to an increase in the production of degradative enzymes, such as lignin peroxidases, laccases, and
manganese peroxidases (Espinosa-Ortiz e t al., 2022). Competition for resources and space as well
as oxidative stress is other effects of fungi and bacteria co-cultivating together (Wan et al., 2015).
Oxidative stress can speed up the transition of fungi to secondary metabolism, which leads to the
creation of oxidative enzymes. In fact, oxidative enzymes called fungal laccases efficiently break down
persistent pollutants (Wan etal., 2015).
It is common k nowledge t hat the presence of ligni nolytic enzy mes in fungi facilitates the deg radation
of pesticides. Most of the time, only a small portion of pesticides are degraded by bacteria. Nonetheless,
it has been documented that both aqueous and porous media may be used to co-culture fungal and
bacterial species to break down organochlorine and organophosphate insecticides (Jain etal., 2017).
In recent years, dichloro-diphenyl-trichloroethane has been the pesticide most frequently utilized in
research on fungal degradation (Va ksmaa etal., 2023). The fungal–bacterial co-cultures showed 86%
dichloro-diphenyl-trichloroethane break down after 712 days of incubation. It was proposed that the
capacity of the used bacteria (Pseudomonas aeruginosa) to create rhamnolipid biosurfactants, which
can improve the solubility of dichloro-diphenyl-trichloroethane, was the cause of the increased break
down by the fungal–bacterial co-cultures (Deshmukh etal., 2016). The same pesticide degradation
process was applied in different research using the fungus Pleurotus eryngii and the bacteria Ralstonia
pickettii, which produce biosurfactants (Purnomo etal., 2020). After seven days of incubation, the
co-culture degraded the pesticide by 78%, whereas the single fungal culture had only degraded it by
43%. The authors noted that the bacteria’s presence stimulated the fungus’s development. Li et al.
(2016) used a co-culture of the fungus Pycnoporus sanguineus and the bacteria Alcaligenes faecalis
to study the break down of sulfamethoxazole. The co-culture degraded sulfamethoxazole to 73% after
48 hours of incubation. The increased elimination effectiveness was attributable to P. sanguineus’s
increased laccase activity when A. faecalis was present (Li etal., 2016).
8.3.3 Enzymes application-based approach
Many yeasts and filamentous fungi, which are well recognized for their environmental durability and
resistance to degradation, have been used to decolorize synthetic dyes, mostly employed in the textile
sector (Deshmukh e t al., 2016; Levin et al ., 2004). Fungal extracellular enzymes, including lignin
peroxidases, laccases, and manganese peroxidases, can degrade synthetic dyes without producing
toxic aromatic amines (Akerman-Sanchez & Rojas-Jimenez, 2021). However, because fungi grow
best at low pH levels, using them in continuously operating reactors typically necessitates lengthy
hydraulic retention times for decolorization, which could be problematic given that the majority of
effluents containing synthetic dyes have an alkaline pH (Akerman-Sanchez & Rojas-Jimenez, 2021).
One potential solution to overcome the pH limitation of fungal extracellular enzymes in decolorizing
synthetic dyes is immobilized enzymes (Somu et al., 2022). Immobilization techniques can help
maintain enzyme activity at higher pH levels, allowing for more efficient decolorization processes.
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146 Detection and Treatment of Emerging Contaminants in Wastewater
Additionally, immobilized enzymes in continuously operating reactors can reduce the hydraulic
retention times required for effective dye degradation (Somu etal., 2022).
Tran et al. (2010) suggested the combination of enzymes isolated from fungi (laccases) and
bacteria (oxygenases) as a plausible strategy to improve the degradation of emerging trace organic
contaminants. For instance, bacterial oxygenase can oxidize aromatic pollutants, resulting in smaller
phenolic compounds (Tran e t al., 2010). These phenols can be toxic to bacteria. However, fungal
laccases can promote the degradation of these phenolic compounds. Therefore, the combination of
fungal and bacterial enzymes can result in a synergistic break down of organic contaminants. In
addition, microbial secondary metabolites like pigments, antibiotics, alkaloids, and carotenoids can
facilitate external interactions among partners in microbial communities (Espinosa-Ortiz eta l . , 2022).
Using the microbial enzyme cytochrome P450 to convert hydrocarbons into less hazardous
chemicals is a novel bioremediation technique. P450s are naturally able to break down xenobiotics
through a variety of bioremediation-related chemical processes, including aliphatic hydroxylations and
epoxidations, dealkylations, dehalogenation, and different mechanism-based inactivations (Bhandari
etal., 2021).
Protease is another enzyme from the hydrolase family that catalyzes the peptide bonds in proteins.
It was isolated from a fungus like Aspergillus sp. Due to their low cost, prolific manufacturing, and
effective action, fungi-derived proteases are of utmost significance. They are extensively employed in
sectors of the economy such as wastewater treatment, the food sector, and the leather sector. Protease
can be utilized in bioremediation for the break down of polymers since it can break down ß-ester
linkages, ß-ester bonds made by poly(hydroxybutyrate)depolymerase, and c-bonds made by lipase (de
Souza etal., 2015).
8.3.4 Genetically modified fungi application-based approach
Although fungi are well known for their role in the removal of pollutants, the capacity of local species
to digest these contaminants is limited, and the process is time-consuming. Hence, the break down
process can be sped up by genetically engineered organisms, whose altered metabolic pathways
stimulate the oversecretion of a range of proteins helpful to the bioremediation process (Maqsood
etal., 2023).
Cur rently, rese arch is bein g done on the widespr ead applicat ion of genetical ly altered m icroorga nisms
that can aid in the removal of ECs from the environment, such as petroleum, naphthalene, toluene,
benzene, and other xenobiotic chemicals (Rafeeq et al., 2023). However, most studies focus on
engineered bacterial species. More research should be done to explore the enzymatic mechanisms of
fungal species.
Fungal strains’ genomic and metagenomic study has given researchers fresh insight into how
to develop and exploit them as biotechnological tools. These omics analyses have assisted in
identifying several taxa of fungi in various environments that are being studied for their potential to
bioremediate (Malik et al., 2022). To break down phenolic substances, the yeast laccase gene from
the fungus Yarrowia lipolytica was inserted into the Pichia pastoris genome (Kalyani etal., 2015).
The yeast laccase gene (YlLac) was extracted from the isolated Yarrowia lipolytica using a modified
thermal asymmetric interlaced polymerase chain reaction. Compared to other known laccases, the
utilization of the engineered yeast demonstrated better catalytic effectiveness toward 2,2-azino-bis(3-
ethylbenzothiazoline-6-sulfonate) and 2,6-dimethoxyphenol. Because of this, the yeast recombinant
laccase was considered a promising candidate for industry use (Kalyani etal., 2015).
Similarly, the expression of the Phanerochaete flavido-alba laccase gene in Aspergillus niger
as well as the physical and biochemical characteristics of the recombinant enzyme (rLac-LPFA)
was studied in order to evaluate it for the biotransformation of synthetic dyes (Benghazi et al.,
2014). High amounts of an active recombinant enzyme (30 mg L-1) was produced by A. niger.
Interestingly, the recombinant enzyme performed better in tests with organic solvents and pH
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147Novel approaches for removing emerging contaminants from sludge
ranges of 2 to 9. Moreover, compared to the native enzyme, synthetic textile dyes showed a greater
proportion of decolorization and biotransformation (Benghazi et al., 2014). These findings suggest
that the expression of the Phanerochaete flavido-alba laccase gene in A. niger has the potential
to be a promising tool for the biotransformation of synthetic dyes. Further research could focus
on optimizing the production and application of the recombinant enzyme for industrial-scale dye
degradation processes.
Investigations were done into the introduction of the yeast strain Kluyveromyces lactis’ Lcc1
laccase in the fungus Trametes trogii. Compared to the native enzyme, the secreted recombinant
laccase had improved enzyme properties. As a result, they were able to draw the conclusion that
particular K. lactis strains with advantageous physiological characteristics and transcription
regulation of the heterologous gene would be the best hosts for the manufacture of laccase isoenzyme
(Ranieri etal.,2009).
The three major categories of gene editing methods are ZFN (Zinc Finger Nucleases), TALEN
(Transcription Activator-Like Effector Nucleases), and CRISPR/Cas (Clustered Regularly Interspaced
Short Palindromic Repeats and Cas9 Protein) (Maqsood et al., 2023). The area of bioremediation is
increasing as a result of scientific concepts on CRISPR toolkits and creating gRNA for the expression
of function-specific genes in non-model organisms. Since they can endure and retain a variety of
hazardous, resistant, and non-degradable xenobiotics, fungi, like bacteria, make attractive candidates
for metabolic engineering and gene editing. The current route is modified using metabolic engineering
to optimize the efficiency of the bioremediation procedure. CRISPR/Cas is a superior gene editing
technique to ZFNs and TALENs due to its high throughput programming capability. In addition,
CRISPR/Cas9 genome editing technology has revolutionized the field of genetic modification by
providing a precise and efficient tool for altering an organism’s DNA (Maqsood et al., 2023). This
technology allowed researchers to target specific genes and make precise changes, such as modifying
the genes that code for hydrocarbon break down or generating hybrid strains. For instance, 20 amino
acid molecules were changed to enhance the dioxygenase’s capability to recognize polychlorinated
biphenyls. Later, it was discovered that switching threonine for aspartic acid might improve the
dioxygenase activity for the oxidation of other substrates (Suenaga et al., 2002). With CRISPR/Cas9,
scientists can now explore new possibilities for enhancing the capabilities of enzymes like dioxygenase,
opening up exciting avenues for improving bioremediation strategies.
At its pinnacle, microbiome engineering using the CRISPR/Cas9 tool for emerging pollutant
biodegradation would make it important to encourage keystone species for workable advancement.
Understanding the functions of microbial genes is based on the application of experimental genetics
to cultured microorganisms. However, most fungi remain uncultivated, preventing the application
of traditional genetic methods to these organisms (Maqsood et al., 2023). A generalizable strategy
for genome editing of specific organisms in microbial communities has been explored through the
application of environmental transformation sequencing (ET-seq), in which untargeted transposon
insertions are mapped and quantified after delivery to a microbial community (Rubin etal., 2022).
Next, DNA-editing all-in-one RNA-guided CRISPR-Cas transposase (DART) systems for targeted
DNA insertion into organisms identified as tractable by ET-seq are used to enable organism- and
locus-specific genetic manipulation in a community context. By testing the fitness of genes and doing
site-specific editing on a variety of non-model bacteria, these methods can be used to increase and
improve the preferred population in the soil, including the fungal population.
In contrast to bacteria, biotechnological innovations’ role in fungal bioremediation is comparatively
less well documented. In addit ion, bacteria a nd fungi show di fferent mechanisms for the bior emediation
of emerging pollutants. Significant progress in molecular biology related to fungi has been achieved,
especially in the extraction of genetic material, gene cloning, and genetic engineering of fungi (Jafari
etal., 2013). A great future lies in successful genetic engineering intending to construct new potential
fungi that can utilize ECs as the sole carbon source and remove them from nature.
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148 Detection and Treatment of Emerging Contaminants in Wastewater
8.4 FACTORS AFFECTING FUNGAL-MEDIATED PROCESSES
Fungal-mediated processes have emerged as promising approaches for the removal of ECs from sludge
and wastewater. However, achieving efficient and effective remediation requires a comprehensive
understanding of the various factors that influence these processes. Several key factors significantly
impact the efficacy of fungal-mediated removal.
The composition and characteristics of the contaminants themselves play a critical role in
determining the success of fungal degradation. The chemical structure, concentration, and stability
of the contaminants can influence the availability and accessibility of the target compounds to
the fungal enzymes (Ashe etal., 2016; Batista-García et al., 2017; Gros et al., 2014; Singh etal.,
2021). Understanding the nature of the contaminants is essential for selecting appropriate
fungal species or optimizing cultivation conditions. During the treatment process, the partition
of ECs from wastewater to sludge is contingent upon various physicochemical properties of the
compounds, including molecular weight, acid dissociation constant (pKa), octanol–water partition
coefficient (KOW), solubility, and biodegradability (Mohapatra et al., 2021). To illustrate, the
sorption of hydrophobic compounds, like PAH, exhibits an increase with higher molecular weight,
hydrophobicity, and the presence of phenolic and aromatic compounds in the dissolved/colloidal
matter (Barret etal., 2010). Specifically, the molecular weight of the compound and the existence of
chlorine atoms enhance the sorption potential due to the presence of an intramolecular hydrophobic
environment (Barret etal., 2010).
Environmental conditions also play a crucial role in fungal-mediated removal processes. pH,
temperature, and oxygen availability directly impact fungal growth, metabolism, and enzymatic
activities. Fungi typically exhibit specific pH and temperature optima for optimal growth and enzyme
production (Ashe etal., 2016; Naghdi etal., 2018; Singh etal., 2021). Deviations from these optimal
conditions can hinder fungal activity and reduce the efficiency of contaminant degradation. In their
study, Esterhuizen et al. (2021) examined the factors influencing the ability of the fungus Mucor
hiemalis and P. chrysosporium to degrade acetaminophen (APAP), a commonly used pharmaceutical
compound that poses a significant environmental concern due to its widespread use and subsequent
presence i n various water bodies. Additiona lly, they noticed that whereas Phanerochaete chrysoporium
demonstrated superior APAP remediation without pH adjustment, Mucor hiemalis’s remediation was
improved by 12% with pH modification. In fact, the acidic environment favored its metabolic activity,
as it produces lignin peroxidase enzymes optimized at pH levels between 4 and 4.5, potentially
contributing to APAP degradation (Esterhuizen etal ., 2021). A recent study conducted by Kang et al.,
(2021) aimed to explore the capacity of Bjerkandera spp. TBB-03 in synthesizing indigenous fungal
enzymes and its effectiveness in breaking down APAP. The findings of this research shed light on the
potentia l of Bjerkandera spp. TBB -03 as a prom ising cand idate for bioremedia tion application s target ing
pharmaceuticals and personal care products. Ligninolytic processes were found to generate radical
intermediates, facilitating radical polymerization and simplifying the precipitation-based removal of
Acetaminophen (APAP). These oxidative coupling processes enabled the rapid polymerization-based
elimination of APAP, irrespective of temperature conditions. The optimal temperature for the removal
of bisphenol A (BPA) was found to be 40°C, as higher temperatures increased the reaction rates of the
catalytic cycle. The removal behavior of three PPCPs at different pH values was assessed, revealing
complete removal of APAP within 2 h at pH 5–7, with the best performance observed at neutral pH
and reduced efficacy at higher pH. In conclusion, TBB-03 laccase effectively regulated the oxidation
of various PPCPs, but its performance and activity were influenced by external factors such as pH and
temperature (Kang etal ., 2021). Thus, maintaining favorable environmental conditions is essential for
maximizing fungal activity and remediation efficiency.
Nutrient availability, particularly from carbon and nitrogen sources, is another critical factor
influe ncing fun gal-mediat ed removal. C arbon sourc es provide the ener gy requi red for fung al growt h and
enzymatic activities, while nitrogen sources are essential for protein synthesis and enzyme production
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149Novel approaches for removing emerging contaminants from sludge
(Nitsche etal., 2013; Peng etal., 2021). In their study, Badia-Fabregat etal. (2015) investigated the
degradation of pharmaceutically active compounds by T. versicolor using 1.5 L air-pulsed fluidized
bioreactors. They discovered that the introduction of external nutrients significantly improved the
degradation capabilities of T. versicolor. Impressive degradation rates ranging from 80% to 100% were
achieved for challenging-to-biodegrade compounds, including diclofenac, ciprofloxacin, ofloxacin,
sulfamethoxazole, furosemide, atenolol, valsartan, and gemfibrozil. In contrast, Esterhuizen e t al.
(2021) found that nitrogen limitation stimulated APAP removal by M. hiemalis, as the fungus allocated
energy to extracellular enzyme production. Therefore, understanding the nutrient requirements of the
fungal species being employed and optimizing the nutrient composition of the growth medium can
enhance fungal growth and remediation potential.
In addition to the target contaminants, environmental conditions, and nutrient availability,
the presence of co-contaminants can influence the remediation process (Mukherjee et al., 2022).
Co-contaminants may include heavy metals, persistent organic pollutants, or other chemical
compounds commonly found in sludge and wastewater. These co-contaminants can interact with
fungal degradation processes, either synergistically enhancing or inhibiting removal efficiency
(Rahman, 2020; Zhou e t al., 2015). Understanding these interactions is crucial for predicting the
overall remediation outcomes and developing strategies to mitigate any potential negative effects.
In conclusion, fungal-mediated processes offer great promise for the removal of ECs from sludge
and wastewater. However, optimizing the efficacy of these processes requires careful consideration
of various factors. By understanding the composition and characteristics of the contaminants,
optimizing environmental conditions, ensuring proper nutrient availability, and accounting for the
presence of co-contaminants, researchers and practitioners can enhance fungal-mediated remediation
strategies. These efforts pave the way for sustainable and effective wastewater treatment approaches,
contributing to the preservation of water resources and environment.
8.5 APPLICATIONS OF FUNGAL-MEDIATED TECHNOLOGY FOR EC REMOVAL
The environmental impact of pharmaceuticals and personal care products is linked to adverse effects
on ecological systems as a consequence of the use of particular inexpensive components. Even at low
concentrations, the presence of pharmaceutical-derived ECs in water can pose a long-term risk to
human health and aquatic ecosystems (Tran etal., 2019).
Antibiotics like ciprofloxacin, erythromycin, roxithromycin, and ofloxacin have been discovered
in quantities as high as 6.7 g/L (Verlicchi et al., 2012), and other drugs detected in effluent waters
include antihypertensives, beta-blockers, diuretics, and lipid regulators, indicating that wastewater
treatment plants (WWTPs) are deficient in the degradation of these compounds (Gogoi etal., 2018;
Jjemba, 2006; Petrović etal., 2003).
Sulfonamides represent the widespread antibiotics used to treat or prevent infectious diseases in
humans, and higher dosages are being used to treat or prevent infectious diseases in livestock and
cattle husbandry (Boxall et al ., n.d.). Their acetylated metabolites have been detected in different
environmental samples, such as influent and effluent wastewater samples, rivers, and sediments,
and they have reached levels up to 1.10 ng/g in the WWTP sludge (Cui et al. 2020; García-Galán
et al. 2011). A significant portion of these wastes is subsequently released into sewage (Cui e t al.,
2020). García-Galán etal. (2011) used a fungal treatment with T. versicolor during the degradation
of sulfamethazine. By the end of the process, the degradation of preexisting sulfonamides was highly
efficient (about 100%), since none were discovered in the treated sludge. In fact, T. versicolor has been
demonstrated to break down the medicines naxopren and carbamazepin (Rodríguez-Rodríguez etal .,
2010) and ibuprofen (Marco-Urrea etal., 2010) obtained from wastewater. In addition, T. versicolor
has lately received attention for its ability to degrade a variety of pharmaceuticals and personal
care products, including nonsteroidal antiinflammatory drugs, lipid regulators, and antiepileptic
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150 Detection and Treatment of Emerging Contaminants in Wastewater
pharmaceuticals (Marco-Urrea etal., 2010). In the current circumstances, the degradation of several
spiking pharmaceuticals and personal care products (naproxen and carbamazepine) by T. versicolor
in sludge cultures revealed interesting results for potential applications (Rodríguez-Rodríguez etal.,
2010). The degradation capacity of T. versicolor was additionally demonstrated in sewage sludge
sterilized systems, where 100% removal was accomplished for sulfamethazine, sulfapyridine, and
sulfathiazole. This demonstrates the potential application of the fungus for bioremediation purposes.
In 2015, a project was conducted by Díaz-Cruz et al . (2015) to investigate the applications of
environmentally friendly technology based on fungal-mediated treatment for the degradation of
ingredients in personal care products, which are frequently detected at relevant concentrations in the
aquatic environment. The reported removal efficacy varied greatly depending on the experimental
setup, organic substance, and kind of fungal. The methods and factors governing fungi break down,
particularly white-rot fungus and their specialized lignin-modifying enzymes, were thoroughly
reviewed and explained. The WRF have been used in water and soil bioremediation processes
(Rodríguez-Rodríguez et al., 2013), and they are composed of an eco-physiological group of fungi
capable of degrading lignin (Hale & Eaton, 1985; Rodríguez-Rodríguez etal., 2013). Due to the low
specificity of this enzymatic machinery, other targets, including a large number of contaminating
compounds such as pharmaceutical compounds and antibiotics, can be degraded (Asgher etal ., 2008;
Cruz-Morató etal., 2013; Marco-Urrea etal., 2010).
Walters et al. (2010) received funding from the National Institute of Environmental Health
Sciences (NIEHS) to report the incidence and loss of various pharmaceutical compounds from
biosolid–soil mixtures subjected to ambient outdoor settings for three years. Some compounds, such
as diphenhydramine, fluoxetine, thiabendazole, and triclosan, showed no detectable loss during the
monitoring period, while others, such as azithromycin, carbamazepine, ciprofloxacin, doxycycline,
tetracycline, 4-epitetracycline, gemfibrozil, norfloxacin, and triclosan, had half-life estimates ranging
from 182 to 3466 days. These findings emphasize the potential use of T. versicolor to lessen the impact
of biosolids once discharged into the environment, perhaps lowering pharmaceutical compound
concentrations in considerably shorter treatment periods.
It has been reported that microbially induced calcite has a high removal efficiency of many divalent
metal cations and radionuclides such as Pb, Cd, Co, and Sr. It is a promising in situ remediation
technology for environmental heavy metal contamination because it is extremely efficient, profitable,
and ecologically acceptable (Fujita et al., 2004; Lauchnor etal., 2013). In fact, Li et al. (2013) used
different isolates to assess their capability for removal of heavy metals including cobalt. It was found
that the isolates could successfully remove the contaminations ranging from 88% to 99% in a short
period of time (24 h). The results show that Sporosarcina sp. and Terrabacter tumescens had the
highest removal for cobalt.
Actually, microbially induced calcite has been wildly investigated by employing bacteria for the
mineralization of heavy metals such as chromium and lead. However, the process of metal remediation
from solutions and soil using fungi is still not entirely defined. In 2017, Qian et al . published one
of the few papers defining fungus-induced calcite precipitation in heavy metal cleanup. The fungal
strain utilized in this study (P. chrysogenum) was isolated from cement sludge and subsequently used
to biomineralize chromate and lead from an aqueous solution (Qian e t al., 2017). As an outcome,
an increase in the carbonate-bound fraction of metals in soil was reported when this fungal strain
was used for metal remediation in soil. In polluted soil, the proportion of exchangeable chromium
decreased from 41.60% to 1.95%, whereas the percentage of exchangeable plomb decreased from
41.27% to 2.19%.
The Engineering Research Council of Canada (NSERC) financed a study related to the reaction
of plants to heavy metal stress and pointed the way to solutions that could make this technology
more viable (Gamalero etal., 2009). As an alternative to traditional physical and chemical methods
of environmental cleanup, scientists have created phytoremediation systems, which use plants
to remove or render harmless a variety of contaminants. Plant growth-promoting bacteria and
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151Novel approaches for removing emerging contaminants from sludge
arbuscular-mycorrhizal fungi can both be used to help with phytoremediation and plant development
in metal-contaminated soils (Gamalero et al ., 2009). As well as that, pesticides containing halogenated
chemicals, such as chlorophenols, were widely utilized in the last century. They are soluble in organic
solvents and only marginally soluble in water (Tomasini & León-Santiesteban, 2019).
Some fungal strains from various taxonomic backgrounds can eliminate, degrade, and even
mineralize chlorophenols in liquid and solid matrices. A study linked 2-CP para-oxidation to the
extracellular laccase activity produced by the white-rot fungus Trametes versicolor, which converted
2-CP into 2-chloro-1,4-benzoquinone (Grey etal., 1998). Laccase has been shown to not only oxidize
2-CP but also polymerize monochlorophenols. Purified laccase from Rhizoctonia praticola was able
to synthesize various dimeric, trimeric, and tetrameric compounds from 2-CP and 4-CP via oxidative
coupling mechanisms (Sjoblad a nd Bollag, 1977). Laccase’s capacity to polymeri ze monochlorophenols
provides the possibility that it may be employed in the production of new substances with potential
uses across a range of sectors. Another study showed the efficiency of the degradation activity of P.
chrysosporium against 2-chlorophenol by allowing the fungus to grow on and into porous support
particles suspended in an agitated fermenter (Armenante etal., 1992).
There have been very few investigations onto the deterioration of ultraviolet (UV) filters in both
liquid and solid media. There needs to be more data on the biodegradation of UV filters by fungi.
Recently, an attempt was made to fill this gap by analyzing the potential of the white-rot fungus T.
versicolor to destroy specific UV filters (Badia-Fabregat eta l ., 2012). Rodríguez-Rodríguez eta l . (2013)
showed high percentages of degradation of several UV filters and some of their metabolites in a solid-
phase treatment of sewage sludge by T. versicolor. The near-complete removal of those compounds was
attributed to fungal biotransformation because the treatments were performed in sterile conditions.
The use of the whole fungus, T. versicolor, to destroy specific UV filters showed that the degradation
mechanisms are only beneficial if they do not result in the formation of new compounds with increased
toxicity or bioaccumulation capacity (Badia-Fabregat etal., 2012; Gago-Ferrero etal ., 2012). To have a
complete picture of the process, it is required to identify and characterize the derivatives made during
the transformation processes, as well as assess the potential toxicity of both the source chemicals and
the degradation products formed.
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© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org /lice nses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0159
Purusottam Tripathy1, Charu Juneja1,2, Abhishek Sharma1,2, Om Prakash1 and Sukdeb Pal1,2*
1Wastewater Technology Division, CSIR-National Environmental Engineering Research Institute, Nagpur 440020, India
2Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India
*Corresponding author: s_pal@neeri.res.in
ABSTRACT
Emerging contaminants (ECs) are pervasive in the environment and have gained more prominence over the past
few years. ECs such as pharmaceuticals, personal care products, endocrine disrupting compounds, and their active
congeners, whose occurrences at trace levels in untreated/treated wastewater are detrimental to human health
and the natural biota. The search for these chemicals’ origins has frequently led to wastewater treatment facilities
as a portal of entry for pollutants into the environment. Emerging pollutants enter wastewater via a variety of routes,
including hazardous spills, farm runoff, excretion via urine and feces, and consumer product disposal and usage.
Another source could be items like shampoo, toothpaste, soap, and disinfection washes which contain biologically
active components that, when used, release these pollutants into the sewage system and are subsequently
transferred to a wastewater treatment plant. Since these contaminants were introduced or detected relatively
recently, there is an existential knowledge gap about their fate, impacts, and behaviors, as well as treatment
strategies for their effective removal. The word “emerging pollutants,” which is frequently used in environmental
debates, refers to new health risks that emerge as a result of microlevel exposure to existing pollutants. Emerging
contaminants have a variety of physicochemical characteristics that influence their exposure, fate, persistence, and
toxicity in the environment. In the present chapter, a brief overview of emerging pollutants, their main categories,
occurrences, points of discharge, and toxicity in natural and engineered systems will be provided, followed by an
illustration of physicochemical properties and detected micropollutant concentrations that have raised concerns
in recent years. This chapter also focuses on existing research that provides credible and quantitative information
on ECs in various water sources, as well as the removal efficacy of different treatment techniques for different
emerging contaminants.
Keywords: emerging contaminants, micropollutant, PPCPs, fate and transport, environment
9.1 BACKGROUND
The extensive prevalence of water and environmental contamination poses a threat to the well-
being and sustainability of the interconnected ecosystems that support all life. The growing concern
Chapter 9
Tracing the pathways: the journey of
emerging contaminants from
wastewater into the environment
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160 Detection and Treatment of Emerging Contaminants in Wastewater
regarding pollution has prompted individuals worldwide to dedicate their efforts to investigating
various types of pollutants, including biological entities like microbes, metallic substances such as
nutrients, heavy metals, and trace organic micropollutants (Chen & Zhou, 2014; De la Cruz etal.,
2012). Over the past few decades, research on the characteristics of wastewater has brought to notice
the environmental presence of numerous newly identified anthropogenic compounds. These trace
compounds, predominantly organic, are commonly referred to as “emerging pollutants”. An emerging
contaminant refers to a contaminant that has a new origin, an alternative pathway to human
exposure, or novel treatment techniques. These contaminants are classified based on their perceived,
potential, or actual risks to the environment and humans. They can be instigated from various
sources such as industrial activities, municipal (domestic) wastewater, agricultural practices, hospital
waste, or laboratory effluents. In aquatic environments, the concentration of emerging contaminants
(ECs) typically shows variation ranging from parts per billion (ppb) to parts per trillion (ppt). The
detrimental effects they have on both aquatic and terrestrial organisms, as well as human health, have
become a matter of concern among experts and the general public. The notable classes of emerging
contaminants encompass pharmaceuticals and personal care products, pesticides, surfactants and
their congeners, nanomaterials, plasticizers, and flame retardants. Certain endocrine-disrupting
chemicals (EDCs) have been recognized as a subset of these emerging contaminants. They possess the
capacity to interfere with the regular functioning of the endocrine system, which is found in a wide
array of organisms, including amphibians, snails, fish, birds, crustaceans, humans, and other species.
However, emerging contaminants are not limited to the aforementioned categories and can also
include nanomaterials (NMs), metabolites of contaminants, engineered genes, illegal drugs, and so
on. The organic trace pollutants, which are not currently regulated are categorized as emerging micro-
pollutants and have been discovered or identified more recently due to advancements in analytical
technologies. Nanomaterials, for instance, have an impact on bacterial biomass during wastewater
treatment, resulting in reduced biological activity and subsequently decreasing the efficiency of
emerging contaminant removal (Wang etal., 2012).
ECs have been detected in various water sources, including groundwater, drinking water, surface
water, and WWTP effluent discharge. These contaminants can be found in all these water reservoirs
and pose potential risks to both the environment and human health (Samaras et al ., 2013; Ya n g
etal., 2014). Municipal wastewater is considered a significant contributor to the release of emerging
contaminants into the environment, along with other sources such as point and non-point sources,
indust ries, stor mwater runoff, domestic wastew ater, and WTP s. Additionally, there is growing attent ion
toward the management of sludge due to the presence of high levels of emerging contaminants in it.
The existing design of wastewater treatment plants (WWTPs) has limitations in effectively removing
emerging contaminants and their metabolites, resulting in their release into rivers or streams. Thus,
there is a need for further research and improvements in wastewater treatment technologies to
address the removal of emerging contaminants. Significant progress has been made in the field of
wastewater technologies concerning nutrient removal. However, the focus on the performance of these
technologies in removing emerging contaminants is still an ongoing area of study (Molinos-Senante
et al ., 2012). Limited data are available regarding the ecotoxicological impacts of ECs on surface water
bodies as well as their removal efficacy in water treatment processes. In wastewater, pharmaceutical
compounds can belong to various classes, including veterinary/human antibiotics, prescribed/non-
prescribed drugs, and certain steroids. PCPs encompass chemicals present in consumer goods, such
as galaxolide and tonalide. EDCs have the potential to disrupt endocrine systems by exhibiting
estrogenic or androgenic activities even at lower concentrations. The environmental presence of
these emerging contaminants leads to disruptions in both physiological and reproductive metabolism,
increasing the risk of cancer, developing antibiotic-resistant bacteria, and enhancing toxicity from
the mixture of chemicals. It is important to note that these pollutants are generally not monitored
extensively and are not currently regulated in potable water sources (Noguera-Oviedo & Aga, 2016).
The current lack of knowledge primarily pertains to the long-term impacts of emerging contaminants,
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161Tracing the pathways: the journey of emerging contaminants
which have been relatively unexplored thus far. Despite the significant discharge of human medicines
and pharmaceuticals into the environment, there is a notable absence of comprehensive controls
for ecological risk assessment. It is crucial to implement effective wastewater treatment processes
before their release into the environment. Therefore, further research is necessary to understand the
occurrence of ECs at lower concentrations (∼ng/L level) in wastewater, their fate and transformation
during wastewater treatment, and their potential implications for drinking water production (Gogoi
etal., 2018).
9.2 EMERGING (MICRO)POLLUTANTS IN THE ENVIRONMENT
ECs encompass a range of inorganic and organic micro-pollutants including pharmaceuticals,
PCPs, polycyclic aromatic hydrocarbons (PAHs), pesticides, surfactants, synthetic organic dyes, per-
fluorinated compounds, heavy metal ions, plasticizers, flame retardants, and more. These compounds
are generated as a result of human activities in various sectors such as domestic, healthcare units,
agriculture, and industry (Goel, 2006). These contaminants widely spread throughout the env ironment
and pose critical risks to both humans and wildlife due to their physicochemical properties. They are
challenging to detect and have diverse activities and sources of production. Even at low concentrations,
their presence can cause disruption in the endocrine system, chronic toxicity, and contribute to the
development of pathogen resistance. The potential adverse effects of these contaminants underline the
need for thorough monitoring and mitigation measures (Houtma n, 2010).
A wide range of chemical and microbial substances, previously not regarded as contaminants,
are currently being discovered in different environmental contexts, including areas where they were
never intentionally introduced. This occurrence can be primarily attributed to their ability to persist
during long-distance transportation. The origins and routes through which these newly identified
contaminants are introduced into the environment are becoming more closely associated with the
waste and wastewater produced by agricultural, industrial, and municipal practices. Despite arising
from similar industrial, commercial, and domestic activities as conventional contaminants, these
pollutants possess distinct characteristics that necessitate changes in the conventional approach to
pollution control and prevention. Chemical micropollutants often originate from the degradation
of organic compounds, leading to the accumulation of persistent metabolites (Kolpin et al., 2002).
Additionally, the disposal of such products into the natural environment contributes to their presence.
Moreover, shifts in agricultural practices toward intensive farming and the application of sludge or
manure on agricultural fields can result in the leaching of pollutants into groundwater and surface
water, thereby posing health concerns (Gavrilescu etal., 2015).
9.2.1 Pharmaceuticals
Pharmaceuticals encompass a diverse range of compounds that can be categorized as acidic, basic,
or neutral. They are commonly used to treat various conditions, including pain, inflammation, and
other medical ailments. The prevalence of pharmaceuticals in the environment varies, with some
compounds like naproxen being prescription drugs, while others like caffeine are found in everyday
consumables such as coffee, tea, and chocolate. Pharmaceuticals play a crucial role in human
healthcare and veterinary medicine, serving purposes such as nutrition, therapy, diagnostic aids, and
preventive medicine. However, the extensive use of pharmaceutical products, including prescribed
and non-prescribed drugs, antibiotics, and hormones has led to their widespread detection in the
aquatic environment, including surface water and groundwater. These pharmaceuticals are significant
emerging organic contaminants that are found in trace amounts in water sources worldwide
(Chinnaiyan et al., 2018). These pharmaceuticals have adverse effects on human health, as well as
on fish farming, livestock, and poultry. While researchers have studied over 3000 chemicals used in
therapeutic products, only a small proportion of these have been examined in the field at ng/L doses.
This knowledge gap raises concerns about the potential negative effects of these pharmaceuticals on
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162 Detection and Treatment of Emerging Contaminants in Wastewater
human health and wildlife. In livestock farming, organic fertilizers such as urine and manure are
used to enhance productivity. However, these substances indirectly impact the environment and can
reach living organisms through food consumption. Frequently mentioned pharmaceuticals found in
wastewater encompass a range of substances such as antacids, analgesics, antibiotics, clofibric acid,
tranquilizers, β-blockers, stimulants, lipid-lowering drugs, steroids, nitroglycerin, antidepressants,
antipyretics, propranolol, salicylic acid, and anti-inflammatory drugs (Richardson & Kimura, 2017).
Synthetic or natural hormones are indeed significant ecological contaminants due to their
androgenic and estrogenic effects on the ecosystem. Both organic and inorganic hormones can
have adverse impacts on the environment. Some examples of these hormones include 17β-estradiol,
17α-estradiol, norethindrone, estrone, equilenin, equiline, estriol, and mestranol. These hormones can
enter the atmosphere through agricultural practices and are not fully eliminated during wastewater
treatment processes. Consequently, they can persist in the aquatic environment, posing risks to aquatic
life and potentially affecting human health as well. The estrogenic and androgenic properties of these
hormones can disrupt the endocrine systems of ecology, leading to adverse effects on reproduction,
development, and overall ecosystem health. Therefore, the presence of hormones in the environment
is a matter of concern and requires attention in terms of pollution control and mitigation efforts.
9.2.2 Antidepressants
Antidepressants belong to a class of pharmaceuticals that impact neurotransmitters, which are
chemicals used by nerves i n the brain to communicate. Neurotra nsmitter s such as serotonin, dopamine,
and norepinephrine play vital roles in this communication process. The mechanism of action for
antidepressants is thought to involve the inhibition of neurotransmitter release or modulation of their
activity. The specific antidepressant compounds are O-dimethyl venlafaxine, venlafaxine, citalopram,
and dimethyl citalopram. Venlafaxine is categorized as a serotonin-norepinephrine reuptake inhibitor
(SNRI) and is frequently prescribed to address conditions such as depression, depression accompanied
by anxiety symptoms, panic disorder, social anxiety disorder, and generalized anxiety disorder in
adults. O-dimethyl venlafaxine, a major active metabolite of venlafaxine, also functions as an SNRI.
Desvenlafaxine, a synthetic form of O-dimethyl venlafaxine, has been approved by Health Canada
since 2009 for the treatment of depression. On the other hand, Citalopram is a selective serotonin
reuptake inhibitor (SSRI) used to manage depression. It is also prescribed for treating conditions such
as premenstrual dysphoric disorder, post-traumatic stress disorder, anxiety disorder, panic disorder,
and obsessive–compulsive disorder. Dimethyl citalopram, an active metabolite of citalopram, also
functions as an SSRI. These antidepressant medications act on the neurotransmitter systems in the
brain to alleviate symptoms associated with various mental health conditions (Wilson & Ashraf,2018).
9.2.3 Personal care products (PCPs)
PCPs encompass a broad range of household chemicals that are commonly used for health, beauty,
cleaning, or odor control purposes. These chemicals can be found in various personal care products
such as hair and skincare products, soaps, sunscreens, cosmetics, fragrances, and lotions. PCPs also
extend to a class of chemicals present in a wide range of consumer goods, including toothpaste and
kitchen utensils. PCPs are typically utilized for their antimicrobial and antifungal properties, serving
to maintain hygiene and prevent microbial growth. These products are used in substantial quantities
worldwide, contributing to the increasing release of these pollutants into the environment. As PCPs
are extensively used in everyday life, their presence in the environment is becoming more significant.
The continuous use and disposal of personal care products contribute to the contamination of water
bodies, soil, and air. It is important to consider the environmental impact of PCPs and explore ways
to mitigate their release and potential adverse effects on humans and ecosystems (Kim etal., 2016).
Indeed, many substances found in personal care products are bioactive and have the potential to
accumulate in the environment and living organisms. These substances can pose risks to both the
environment and human health. The bioactive nature of PCP substances means that they can interact
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163Tracing the pathways: the journey of emerging contaminants
with biological systems. This can lead to various ecological effects when these substances are released
into the environment. For example, certain PCP compounds may disrupt the endocrine system of
organisms, interfere with reproductive functions, or cause toxicity in aquatic organisms. Additionally,
the bioaccumulative nature of these substances means that they can build up in the tissues of organisms
over time. This bioaccumulation can occur through various pathways, such as ingestion or absorption.
Over time, the accumulated levels of PCP substances can reach concentrations that are harmful to
both the ecosystem and humans. The potential harm to the environment and humans emphasizes the
need for responsible use, disposal, and regulation of PCPs. It is important to consider the potential
long-term effects and to explore alternatives that are less harmful to the environment and human
health (Claudia & Magrini, 2017). The potential emerging pollutants in personal care products (PCPs)
include antiseptics, perfume pollutants such as ultraviolet (UV) filters, galaxolide, preservatives like
diethyl phthalate, pest repellants and disinfectant pollutants like Triclosan (TCS) and triclocarban
(TCC). TCS and TCC are commonly found in wastewater samples at higher concentrations. These
substances are antibacterial and antifungal agents that are widely used in consumer goods like
toothpaste, soaps, body washes, and disinfectants. These products typically contain between 0.1%
of TCS and 2% of TCC by weight (Gatidou etal., 2007). TCS and TCC exert their effects on bacteria
by interacting with the enoyl-acyl carrier protein reductase enzyme (ENR), which is present in their
cell membrane. This interaction inhibits the synthesis of fatty acids. Parabens, including methyl,
ethyl, butyl, propyl, benzyl, isobutyl, and isopropyl hydroxybenzoates are antimicrobial preservatives
commonly used in cosmetics, pharmaceuticals, and certain food products (North, 2004).
9.2.4 Polycyclic aromatic hydrocarbons (PAHs)
PAHs are abundant compounds that occur naturally in fossil fuels (Cao eta l ., 2017). The incomplete
combustion of wood, coal, gas, and oil is also one of the primary sources of PAHs. PAHs are
recognized for their ability to undergo bioconcentration, leading to their rapid entry into the food
chain (Yang e t a l . , 2022). The United St ates Environmental Protection Agency (US EPA) has cla ssified
16 specific PAHs as significant contaminants of concern (Li et al., 2019). PAHs are persistent
compounds due to their lipophilic (fat-loving) and hydrophobic (water-repellent) characteristics.
These properties enable them to remain in the environment for extended periods. PAHs have low
volatility, making them resistant to burning, and non-biodegradable. As the molecular mass of PAHs
increases, their solubility in an aqueous solution decreases logarithmically. PAHs with five or more
rings, due to their lower solubility and low volatility, are commonly found in a granular form. They
tend to be attached to contaminated soil, air, or sediment particulates. On the other hand, PAHs
with fewer rings are more easily soluble in water, making them readily available for biological
uptake and degradation. In general, PAHs with higher numbers of rings are more persistent in the
environment compared to those with lower rings. The increased molecular complexity of higher
ring PAHs contributes to their reduced solubility and resistance to degradation, leading to their
longer persistence in environmental systems
9.2.5 Phthalate esters (PAEs)
PAEs are frequently employed as additives to enhance the flexibility of specific polyvinyl chloride
(PVC) resins. They are also utilized in various other resins like cellulose, polyurethanes, and vinyl
acetat e. The low volatility, fluidit y, and st ability of phthalate esters make them wel l-suited as plasticizers
(Jorgensen, 2008). Phthalate esters are derived from phthalic anhydride and are blended with plastics
to enhance properties such as plasticity, resilience, and transparency (Thomas & Brogat, 2022). These
derivatives find applications in various end-user products, including agricultural adjuvants, resin
houses, toys, cosmetics, soaps and laundry detergents, and more. PAEs are characterized by their poor
water solubility, which plays a crucial role in their biodegradability, aquatic toxicity, and distribution
in the environment. Despite their low solubility, PAEs can be readily absorbed by organic residues
and solid surfaces in environmental systems. This slow and continuous accumulation and release of
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164 Detection and Treatment of Emerging Contaminants in Wastewater
PAEs can have implications for the ecological conditions of water systems. The presence of PAEs in
wastewater treatment facilities and sludge-amended soils is also affected by this phenomenon. Given
their widespread use, the accumulation of PAEs in various compartments of ecosystems has become a
concern. In agricultural soils, the accumulation of PAEs can lead to contamination of the food chain,
including vegetables, and result in indirect or direct human exposure (Vickers, 2017).
9.2.6 Pesticides
Pesticides encompass a collection of organic pollutants categorized according to their distinctive
physiochemical properties, which include fungicidal agents, herbicidal compounds, bacteriostatic
substances, and insecticidal compounds. These substances are widely employed in the agroindustry
to manage and regulate harmful insects, weeds, and microorganisms, among other factors. Nowadays,
pesticides are often detected in groundwater which leads to toxicity, and health effects on living
beings due to their high octanol–water (Kow > 3) values. Generally, dichloro di-phenyl tri-chloroethane
(DDT) and hexachlorocyclohexane are the most consuming pesticides rather than those of phorate,
chlorpyriphos, Atrazine, methyl parathione, and Bentazone (Poonia etal., 2021).
9.2.7 Endocrine active compounds
EACs are a diverse group containing both natural and synthetic compounds that have the ability to
disrupt hormone systems in animals’ bodies. The identification and control of detrimental effects
caused by estrogenic pesticides and drugs (known as xenoestrogens) in living beings commenced
during the mid-1900s. In the late 1980s and early 1990s, substantial evidence emerged regarding
the endocrine-disrupting effects on reproductive systems caused by human-derived xenoestrogens
present in wastewater effluents, even at nano-scale concentrations measured in parts per billion and
parts per trillion (Watkinson et al., 2007). Various studies have been done on the commotion of
sex determination and rations, transformation in procreant behavior, and contraceptive-like actions
in both sexes. Comparable disruptions have also been reported in amphibians, reptiles, birds, and
mammals through various pathways of exposure. Research on accidental exposures and correlative
studies examining the impact of estrogenic compounds found in meals, synthetic polymers (plastics),
PPCPs, and other sources have been conducted on cultivated cells, gnawing, and humans. It has
been observed that developing organisms, including the human fetus, exhibit greater sensitivity to
exogenous estrogenic chemicals compared to adults (Yu eta l., 2009). Research conducted on gnawers
and humans has shown that a single exposure to estrogenic compounds during growth not only affects
the exposed generation but also induces enduring alterations that can be inherited by subsequent
generations, without requiring additional exposures.
9.2.8 Surfactants and food additives
Surfactants, which come under synthetic organic compounds, are used globally in the production
of domestic and commercial goods such as emulsifiers, cleaning agents, dyes, pesticides, and PPCPs
(Mandaric et al., 2016). Surfactants are classified into three categories based on their chemical
properties: cationic, anionic, and dipolar surfactants. High global demand has led to significant
production of surfactants such as lignin, benzene sulfonates, and alcohol ethoxylates. Synthetic
sweeteners like saccharin and sucralose, which find extensive usage in food products, PPCPs, enter
wastewater primarily through human excretion. Metabolized sweeteners not only pose environmental
pollution but also exhibit long-term persistence, contributing to their persistency impact (Mahmood
etal., 2022).
9.2.9 Musks
Musks are a group of compounds renowned for their aromatic qualities. They are widely utilized
across various cosmetics and detergents. Musks are classified into three classes: aromatic nitro,
polycyclic, and macrocyclic musks. Polycyclic musks are used in cleansing products such as shampoos,
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165Tracing the pathways: the journey of emerging contaminants
hair care, and detergents. Polycyclic musks are applied topically to human skin, their subsequent
release into the environment occurs without undergoing any metabolic alterations. Cosmetics, being
extensively utilized among these products, can pose a potential risk to human beings, wildlife, and the
environment, even when present in low quantities (Wilson & Ashraf, 2018).
9.3 EC IN AN AQUEOUS ENVIRONMENT
9.3.1 Classification and sources of EC
Approximately 70% of the numerous ECs identified in samples belong to the category of
pharmacologically active chemicals and PPCPs, while the remaining 30% comprise industrial
and agrochemical substances (Das etal., 2017). Globally, more than 200 pharmacologically active
chemicals have been detected in river streams, with the highest documented abundance being 6 ppm
for ciprofloxacin (Hughes etal., 2013). Moreover, tamoxifen was identified between 25 and 38 ng/L
in river streams (Ferrando-Climent et al., 2014). Jones and group detected multiple antibiotics,
hormones, antidepressants, lipid regulators, analgesic compounds, and chemotherapy drugs in the
range between 0.04 and 6.3 µg/L. In contrast, commonly used chemicals such as sunscreen agents
and preservatives are frequently detected at concentration levels exceeding 1000 ng/L (Petrie etal.,
2015). Kasprzyk–Hordern and group detected 4-benzophenone (sunscreen agent) within the spectrum
of 3597–5790 ng/L (Kasprzyk-Hordern etal., 2009). However, several ECs have been found to have
EC50 values below 1 mg/L. Based on their EC50 values, these contaminants are classified as harmful
to aquatic organisms when the EC50 ranges from 10 to 100 mg/L, toxic when it ranges from 1 to
10 mg/L, and highly toxic when it is below 1 mg/L.
ECs have various pathways to enter aquatic and subsurface environments, which could be
categorized into five main sources: domestic, industrial, hospital, and agrochemical wastes.
Domestic wastes are found to be one of the prominent sources of PPCPs in the environment.
The metabolized drugs inside the human body could come to water and wastewater systems via
human urines and feces. Additionally, human activities contribute to the introduction of PPCPs
into the environment, including substances like cleansing agents, sunscreen, toothpaste, and
various others. However, the production units including PPCPs, biocides, and agrochemicals
are significant sources of ECs in the environment. Additionally, clinical effluents contain drugs,
ARGs/genes, and pharmaceutical byproducts are also major contributors to ECs. Livestock rearing
and cultivation activities are additional significant contributor to ECs, especially in terms of
hormones and biocides employed for enhanced productivity (Barbosa et al., 2016). Additionally,
landfill leaching, irrigation activities, and aquaculture discharge significantly contributed ECs in
surroundings. Table 9.1 summarizes the functions, occurrence, and adverse effects of emerging
contaminants present in the environment.
9.3.2 Occurrence of EC in different water matrix
Significant disparities in the levels of ECs across various aquatic systems have been documented,
primarily attributable to factors such as dilution, persistency, treatment effectiveness, and other
variables. It was observed that ECs are omnipotent in various water systems such as wastewater,
sewage, sludge, ground, surface water, and potable water. During morning period a significant increase
in antibiotic concentration was observed, which was attributed to the accumulation of ingested drugs
in urine during sleep, indicating an intra-day variation (Coutu e t al., 2013). Similarly, an elevated
bioactive byproduct of cocaine was identified on weekends in European countries. However, seasonal
variation of ECs in wastewater was compared, and observed that a substantial concentration of
sunscreen agents and pholcodine was found in summer and cold, respectively (Petrie et al., 2015).
The majority of ECs in treatment systems were found to occur within the concentration range of
0.1–10 µg/L. However, the concentration of ibuprofen and caffeine occurred in between 3.73–603 and
50 µg/L, respectively (Luo etal., 2 014; Zhou etal., 2010).
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166 Detection and Treatment of Emerging Contaminants in Wastewater
Table 9.1 Occurrence and effects of emerging contaminants in the environment.
ECs Function Sources Concentration
of EC in WWTP
Effluent (ng/L)
Removal
Efficiency
(%)
Adverse Effects
Antibiotics
(sulfonamides,
clarithromycin,
roxithromycin,
tetracycline,
penicillin)
Antimicrobial substances
are agents that prevent
infection by either destroying
or impeding the growth of
bacteria
Domestic wastewater,
industry effluent,
pharmaceutical,
hospital effluent,
effluent from aqua
culture, and livestock
farms
42–276 <0–99 Induce antibiotic resistance in
microbial strains, modify the
structure of microbial communities,
and lead to decreased populations
of algae, bacteria, nematodes, and
other organisms
Fire retardants
(polybrominated
diphenyl ethers
(PBDEs))
Utilized in various
applications such as paints,
plastics, televisions, and
building materials to increase
the resistance and make them
less prone to catch fire easily.
Domestic wastewater
and industrial
effluent
1–150 86–96 Impact the brain and nervous
system, disrupt hormone activity,
and influence reproduction and
fertility
Endocrine-
disrupting
chemicals (EDCs)
(Bisphenol
phthalates)
Group of chemicals used
as plasticizers, plastics,
industrial lubricants/solvents,
and so on.
Drinking water,
surface water,
sediments, secondary
sludge and soil
331 32–100 Interfere with the endocrine system,
exhibit estrogenic effects in rats,
result in feminizing side effects in
men, and can contribute to birth
defects and developmental delays
Nonsteroidal
anti-inflammatory
drugs (ibuprofen,
diclofenac)
Reduce inflammation, pain,
and fever
394 –647 <0–98 Associated with an increased risk
of gastrointestinal ulcers, kidney
diseases, and gill alterations in
rainbow trout.
Lipid regulators
(gemfibrozil
clorfibric acid)
Regulation of levels of
cholesterol and triglycerides
in the blood
5. 3 –137.7 27.7–71.8,
0–100
Inhibit bioluminescence and impede
the growth of microalgae.
Beta-blockers
(metoprolol,
atenolol)
Management of abnormal
heart rhythms involves the
inhibition of the hormones
adrenaline and noradrenaline
166 –843 <0–96,
<0–58.7
They affect the reproduction and
growth of fishes, inhibit receptor
discharge in the gills, and have
an impact on breeding cycles and
activity rhythms in trout.
(Continued)
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167Tracing the pathways: the journey of emerging contaminants
Anticonvulsants
(carbamazepine)
Treat epileptic seizures and
mood disorders
482 0–83 Induce oxidative stress in rainbow
trout and have an impact on the
central nervous system
Hormones
(testosterone
est rone)
Coordination and control
of various hormones and
signaling pathways to ensure
proper metabolic function,
stable internal conditions,
and appropriate progression
of sexual maturation.
Domestic wastewater,
Hospital effluent,
Sewage treatment
plants
2–15 0 –100 Affects fertility and reproduction,
feminization of males,
masculinization of females, and
reduced fertility in fish.
Polyaromatic
hydrocarbons
(PAH) (pyrene
anthracene)
Used in the manufacture of
pesticides, plastics, dyes, and
so on.
Agricultural runoffs,
sewage treatment
plants, surface water,
sediments and soils
14–4700 63–69 Cardiovascular diseases,
carcinogenic effects, and poor fetal
development
Per-fluorinated
alkylated
substances
(PFAs) (per-fluoro
octanoic acid)
Used in paints, emulsion
polishes, polymerization and
coatings
15–<1500 ∼95 liver damage, Thyroid disease,
kidney cancer, developmental
effects on an unborn child, and
reduced response to vaccines
Nano materials
(nanocomposites,
nanoparticles)
Used in a variety of, products,
manufacturing processes,
and healthcare.
Industrial effluent — — Affects respiratory systems, poses
risks to wildlife, and contributes to
environmental toxicity.
Viable but
nonculturable
microbes (Vibrio
cholerae, Ye rsi ni a
pestis)
Significant implications
in pathogenesis and
bioremediation
Aquaculture effluent,
Agricultural runoff,
and surface water
— — Affect the gastrointestinal systems
and immune systems, and they
are toxic to the environment and
wildlife
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168 Detection and Treatment of Emerging Contaminants in Wastewater
9.3.2.1 Surface water
The concentration of ECs in surface water is found to be lower than WWTP effluents due to the
dilution of ECs. Rainfall exerts a dual influence on the concentration of ECs in surface water. On the
other hand, rainfall is also subjected to higher ECs via chemical leaching from paints, building and
pavement materials, and sewage runoff due to flash floods. African surface water consisted of multiple
pesticides which varied from 0.06 ng/L to 9 µg/L, respectively (K’oreje etal., 2020).
9.3.2.2 Groundwater
The presence of ECs in groundwater is found to be lower as compared to surface water. There
are various point and non-point sources such as landfill leachate, infiltration from farming areas,
aquifer recharge using non-potable water, and percolation from sewage systems are the main sources
of groundwater contamination (Luo etal., 2014; Stepien etal., 2013). The octanol–water partition
coefficient (Kow) plays a crucial role in determining the extent of groundwater pollution. This is
because the soil serves as the core dissemination pathway for ECs to reach the groundwater. Usually,
the log Kow value of less than 2.5 indicates high hydrophilic mobility of ECs. If the log Kow falls
between 2.5 and 4, it signifies medium mobility. On the other hand, a log Kow value greater than four
suggests low mobility or high retention of ECs within the soil matrix. Triclosan having a high log Kow
value (>4), conserved within the soil, while Trimethoprim, with a lower log Kow value (<1.5) leached
to groundwater (Dougherty etal., 2010; Petrie etal., 2015). Corresponding to surface water, various
PPCPs such as caffeine, sulfamethoxazole, and carbamazepine were also detected (<100 ng/L) in
groundwater (Luo et al., 2014). In South African countries, substantial amounts of paracetamol
(18 µg/L) and nevirapine (1.6 µg/L) were detected in groundwater. Similarly, steroid hormones are
also detected in groundwater in US land sites (Karnjanapiboonwong etal., 2011).
9.3.2.3 Drinking water
Due to the fact that the majority of ECs are not detectable in drinking water, there is a scarcity of
publications available on this topic. Various treatment systems employed in the purification of potable
water are believed to play a crucial role in maintaining the ECs under non-detectable limits. Alike to
groundwater, the majority of ECs detected in drinking water are generally present below 100 ng/L.
However, the concentration of non-phenol (100 ng/L) and carbamazepine (600 ng/L) was detected
lower than PNEC values of 330 and 25 000 ng/L, respectively (Kleywegt etal., 2011). Most of the ECs
in drinking water are detected at permissible limits, it is important to note that potential detrimental
effects from synergistic interactions and transformed by-products of these contaminants cannot be
overlooked. Therefore, regular monitoring and examination of the potability of drinking water is
necessary to ensure the well-being of consumers.
9.3.2.4 Wastewaters
The release of treated wastewater from WWTPs stands as the main contributor to the presence of
ECs in the environment. Unfortunately, most treatment methods are not engineered to eliminate ECs,
leading to their release into the surface water system. Arou nd 70 pharmaceutical compou nds, including
NSAIDs, β-blockers, antidepressants, and carbamazepine, have been extensively studied. These
compounds are widely prescribed, with annual usage exceeding 1000 kg, and can be found in influent
wastewater from various sources. The removal of these pharmaceuticals during wastewater treatment
exhibits a wide range, with some experiencing low removal rates of less than 50%, while others achieve
high removal rates exceeding 80%. This variation can be attributed to the diverse physicochemical
properties of the compounds and their varying susceptibility to biological degradation processes. Due
to partial removal during wastewater treatment, pharmaceutical compounds are frequently detected
in receiving surface waters at concentrations ranging from nanograms per liter (ng/L) to milligrams
per liter (mg/L). Fifteen illegal drugs and legal stimulants were identified in wastewater out of which
tramadol concentration was found to be highest, that is, 7731 ng/L (Kasprzyk-Hordern etal., 2008).
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169Tracing the pathways: the journey of emerging contaminants
However, the widespread social unacceptability of illicit drugs within the community greatly reduces
the likelihood of their presence in the water treatment system. The hallucinogen like C11H15NO2 and
the stimulant C17H21NO4 were identified in riverine systems at concentrations of 25 and 17 ng/L,
respectively. On the other hand, the high usage of licit chemicals in the community frequently
contributes to ECs in water systems. Most studies conducted on EC analysis primarily focus on the
aqueous phase, which involves analyzing pre-filtered samples. However, there has been a notable lack
of measurements made on the particulate phase, such as sludge or suspended particulate matter.
9.3.2.5 Other matrix
In contradistinction to the dissolved phase, emerging contaminants in particulate phases such as
biosolids (sludge) have rarely been documented. This is likely attributed to the complex composition
of sludge and the absence of highly sophisticated analytical methods capable of detecting ECs within
the sludge matrix. The utilization of sludge as a fertilizer is a prevalent practice in the agriculture field
and currently, there are no regulations in place to oversee the application of sludge on agricultural
land concerning emerging contaminants. As a result, ECs in the sludge matrix have the potential to
contaminate the groundwater and soil. Hence, obtaining information regarding the presence and
distribution of these contaminants in such matrices is crucial for formulating an effective strategy
for sludge management. The concentrations of the designated contaminants in the sludge varied
between 0 (below the limit of detection) and approximately 5000 ng/g of the dry weight of the sludge.
The concentration of emerging contaminants is highly influenced by their pattern of usage, and
physicochemical properties such as ionization state and hydrophobicity (Tran etal., 2018). To cite an
instance, hydrophobic emerging contaminants such as miconazole and bisphenol A have been found
in higher concentrations in the sludge matrix attributed to their affinity for the particulate phase.
On the other hand, ciprofloxacin (fluoroquinolones) is absorbed into sludge through the coulombic
interaction, as they exist as zwitterions under environmental pH conditions ranging from 6 to 8.
Additionally, the higher concentrations of ibuprofen in sludge can be attributed to the hydrolysis of
its conjugates. The anaerobic digestion of sludge has been proven to be an effective process reducing
the concentration of ibuprofen as well as other extensively studied emerging contaminants such as
carbamazepine, ketoprofen, ethinylestradiol, and so on (Martín etal., 2012).
9.3.3 Pathways of ECs
Once released into the environment, ECs undergo various natural modification processes, such as
photolysis, dispersion, transformation, and adsorption onto suspended particles. These processes
contribute to the reduction of EC concentrations in surface water bodies (Pal etal., 2010). However,
traditional W WTPs lack effective treatment strategies to address the entry of ECs into the system.
Consequently, partially degraded, or unchanged ECs find their way into aquatic systems via the
discharge of effluent and sludge from WWTPs s after treatment (Luo etal., 2014; Pesqueira eta l . , 2020).
Moreover, the utilization of treated wastewater for agricultural practices substantially introduces ECs
into the soil, leading to further uptake of these contaminants by the crops (Paz etal., 2016). Because
soil, groundwater, and other environmental matrices are interrelated, the occurrence of emerging
pollutants in any of the domains can have an accumulative and detrimental effect on the entire
environment. As a result, WWTPs are regarded as one of the main anthropogenic sources that emit
emerging contaminants into the surroundings, in addition to industrial discharges, hospital effluents
agricultural runoffs, aquaculture effluents, and landfill leachates. Without proper identification and
implementation of appropriate treatment technologies, the management of emerging contaminants is
compromised, thereby posing a risk to the sustainable utilization of treated wastewater.
The environmental fate of emerging contaminants can be evaluated using the source-path-receptor
model, which also facilitates the risk assessment of target receptors. Figure 9.1 illustrates various
pathways of emerging contaminants originating from different sources. Emerging contaminants
predominantly derive from industrial effluents, agricultural runoff, effluent from hospitals,
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170 Detection and Treatment of Emerging Contaminants in Wastewater
wastewater from laboratories, leachate from landfill disposal sites, and to a lesser extent, domestic
wastewater. Domestic sewage comprises partially metabolized or unmetabolized pharmaceutical
and personal care products (PhACs) that are excreted by humans. Furthermore, the occurrence
of emerging contaminants in water bodies is influenced by the population’s consumption patterns.
Conventional WWTPs also release emerging contaminants in the effluent as they are inadequate
for effectively treating such pollutants. Septic tanks and landfill sites are marked by the presence
of highly concentrated leachate, which is the major contributor to emerging contaminants in
groundwater. This is particularly notable in areas where the aquifers have a high percolation rate
and the groundwater table is less deep (Ramakrishnan etal., 2015). Additionally, the employment
of fertilizers and other chemicals in agricultural practices is another major factor leading to the
contamination of groundwater and surface water. It is important to note that most emerging
contaminants are highly distributed in the environment and are resistant to biodegradation or
hydrolysis under normal environmental conditions. Ebele’s team conducted a study that revealed
elevated concentrations of pharmaceuticals and personal care products (PhACs) in various organisms
such as goldfish (Carassius auratus), snails, and mosquitofish (Gambusia holbrooki) (Ebele et al.,
2017). These findings suggest the potential biomagnification of ECs within aquatic ecosystems after
being released into the environment.
9.4 GLOBAL OCCURRENCE OF SOME IMPORTANT ECS
ECs typically consist of elements such as nitrogen, hydrogen, carbon, fluorine, sulfur, and fluorine.
The presence, behavior, and movement of ECs in the environment are influenced by various factors,
including water characteristics, sources of contamination, climatic conditions, available treatment
Production in industries
{PhACs, PCPs, Pesticides}
Domestic Agricultural
WWTP
WTPNatural streams/ River
Landfill
Leachate
Treatment
Groundwater
Liquid waste
Runoff
Sludge
Solid waste
Infiltration
Leachate
Products
Solid wasteLiquid wasteHigh
Concentration
of ECs
Lower
concentration
of ECs
Hospitals
Pathways of ECs,
Unauthorized discharge,
Supply from WTP
Wastewater treatment plantWWTP -
Water treatment plantWTP -
Figure 9.1 Schematic representation of emerging pollutants’ origin and pathways with their varied concentration
from the source to disposal locations.
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171Tracing the pathways: the journey of emerging contaminants
methods, physicochemical properties of the compounds, and, socioeconomic factors (Vickers, 2017).
Among all ECs, pharmaceuticals and personal care products (PhACs) are the most commonly
detected contaminants, often found in higher concentrations. This is primarily attributed to their
polar nature and substantial use by consumers, which enables them to persist in the environment
and exhibit greater mobility. It was reported that in 2020, over 50% of the world population will
be dependent on compulsory medicine consumption daily (Aitken & Kleinrock, 2015). According
to Statista, the maximum sales of pharmaceuticals were observed in North America followed by
Europe. Among different analgesics, ibuprofen was reported with a higher concentration in North
America (75.8 µg/L) as compared to Asia (26.45 µg/L), Australia (10.3 µg/L), and Europe (33.76 µg/L)
in the influent of WWTPs. Naproxen was found in the range of 0.08–25 µg/L, in countries like USA,
India, China, Northern America, and different European countries (Mandaric etal., 2017; Singh etal .,
2014; Vickers, 2017). Whereas, the anti-inflammatory drug diclofenac has been detected in municipal
wastewater ranging from 0.11 to 25.68 µg/L with a mean value of 2 µg/L. High ketoprofen (16.2 µg/L)
concentration was found in WWTP influents in India. In 2020, it was reported that more than 50% of
the global population would rely on regular medication consumption (Aitken & Kleinrock, 2015). As
stated in Statista data, the highest pharmaceutical sales, followed by those in Europe, were recorded
in North America. When different analgesics were investigated in WWTPs, ibuprofen exhibited higher
concentrations in North America (75.8 µg/L) compared to Asia (26.45 µg/L), Australia (10.3 µg/L),
and Europe (33.76 µg/L). Naproxen, another commonly used medication, has been found in the range
of 0.08–25 µg/L in nations such as India, Northern America, USA, and China, Northern America,
and various European countries. Additionally, the anti-inflammatory drug diclofenac was detected in
municipal wastewater with concentrations ranging from 0.11 to 25.68 µg/L, with an average value of
2 µg/L. Notably, India exhibited a high concentration of ketoprofen (16.2 µg/L) in WWTP influents.
9.5 FATE OF ECS IN ENVIRONMENTAL WATERS
9.5.1 Human metabolites
Parent compounds are frequently eliminated from the human body alongside various accompanying
metabolites. To illustrate, ibuprofen is discharged in its unaltered drug form (1%), along with
multiple metabolites: (+)–2–4′-(2–Hydroxy-2-methylpropyl)-phenyl propionic acid (25%), (+)-2–40-
(2–carboxypropyl)-phenyl propionic acid (37%), and conjugated ibuprofen (14%) (Kasprzyk-Hordern
etal., 2008). It has been investigated during preliminary studies involving raw sewage samples and
activated sludge samples for steroid estrogens (17α – EE2 3-glucuronide, estriol 16α-glucuronide, and
estrone 3-glucuronide) (Gomes et a l., 2009), the presence of carbamazepine was majorly detected
(Vieno etal., 2007). Moreover, it is imperative to analyze metabolites due to their potential occurrence
at significantly higher concentrations than the respective parent chemical, and their potential
pharmacological activity. A primary metabolite of carbamazepine, namely carbamazepine epoxide,
was detected in the influent of wastewater at concentrations ranging from 880 to 4026 ng/L, on
the other hand, the parent compound was found at levels below 1.5–113 ng/L (Huerta-Fontela etal.,
2010) and these substances can persist even after the secondary wastewater treatment. Given their
discharge into the environmental matrix and the potential for further bio-transformation into the
parent environmental compound, it is imperative to determine these metabolites to accurately assess
the associated ecological risk.
9.5.2 Microbial transformation
Numerous emerging pollutants experience microbial-mediated transformations during secondary
treatment as well as in the natural environment. Biodegradation is commonly considered as the
primary pathway for the elimination of certa in emerging contam inants from water systems (wastewater
and surface waters). Nevertheless, it can lead to the generation of various transformation products.
Unfortunately, these products have not been extensively investigated due to the limitations of screening
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172 Detection and Treatment of Emerging Contaminants in Wastewater
approaches employed for known compounds, such as low-resolution mass spectrometry utilizing
triple quadrupoles technology, which could not effectively identify these products. Additionally, the
scarcity of available standards for these transformation products is attributed to the limited knowledge
regarding the bio-transformation pathways associated with them. In the laboratory-scale studies of
activated sludge, Helbling etal. successfully detected previously unexplored biological transformation
products for several pharmaceuticals, namely valsartan, bezafibrate, diazepam, oseltamivir, and
levetiracetam through the utilization of high-resolution mass spectrometry employing linear ion trap-
orbitrap technology (Helbling etal., 2010). Furthermore, degradation products have been detected
at naturally occurring concentrations in the effluents of activated sludge. In a study, a non-targeted
screening approach using quadrupole time of flight (QTOF) mass spectrometry was employed to
successfully detect transformation products of acetaminophen (P-aminophenol) and azithromycin
(Gomes etal., 2009). The identification of these transformation products is of utmost importance as
they exhibit higher toxicity compared to the parent compound, as exemplified by P-aminophenol.
Hence, the removal of the parent environmental compound does not guarantee the elimination of
its associated toxicity. Despite various parent compounds are found in wastewater, it is plausible to
anticipate the presence of various transformation products in the effluent as well as the receiving
water systems.
9.5.3 Physicochemical processes
Physical–chemical processes can also aid in the removal of EC from surface and wastewater. During
wastewater treatment, removal from the aqueous phase will take place on biomass, or when present
in the river environment, by discharge to sediments. This is most likely accurate for a small number of
ECs, though. For example, if a state of equilibrium is achieved between biomass or sediment and the
aquatic environment for a specific environmental contaminant (EC), there will be no net exchange
between the two phases and no removal from the aqueous phase. Consequently, sorption is not effective
in eliminating them. Studies have demonstrated this for certain ECs like steroid estrogens in activated
sludge processes (Petrie etal., 2014). However, antibiotics such as ofloxacin and ciprofloxacin, due
to their strong affinity for solid organic matter, are removed through sorption during wastewater
treatment (Petrie et al., 2014). Hence, understanding the influence of physicochemical parameters
on the sorption of these ECs is crucial. Additionally, the impact of dissolved organic matter on the
fate of ECs in the environment must be considered, as the binding to dissolved organic materials can
aid in retaining ECs in the aqueous phase of environmental matrices. Furthermore, the development
of organic matter complexes containing EC may prevent the EC from being recognized during
analysis. ECs are subject to photolysis when they are present in an aqueous environment. In river
water, photolysis has been demonstrated to effectively break down several ECs, including naproxen,
ketoprofen, E2, propranolol, EE2, ibuprofen, and gemfibrozil. Ketoprofen’s half-life was 4 min, while
gemfibrozil and ibuprofens were 15 h. This spectrum of susceptibility to photolysis breakdown is
explained by variations in their bond formation. For example, the presence of two aromatic rings in
the carbonyl moiety of ketoprofen results in the formation of a highly reactive triple state, making it
susceptible to breakdown through photolysis. As a result, photolysis can be instrumental in removing
numerous (ECs) from surface waters. However, it is important to note that the degradation of the
parent compound through photolysis does not guarantee complete mineralization, and various
transformation products can be formed, similar to those produced through biological degradation.
Therefore, the absence of the parent molecule may not result in a decrease in toxicity. It is possible
to hypothesize that the presence of particles and dissolved organic matter in environmental waters
will slow down the rate of EC deterioration by reducing the brightness of the sun. Depending on the
par ticular EC, hu mic acid (a tiny molecu lar weight char ged molecule) either slowed dow n or accelerated
the rate of decomposition (West & Rowland, 2012). Indirect photolysis may be the cause of increased
deterioration when humic acid or nitrates are present. Wastewater contains OH radicals and organic
materials (triplet excited state), which makes some ECs more amenable to indirect photolysis (Ryan
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173Tracing the pathways: the journey of emerging contaminants
etal., 2011). Further research is needed to determine the effects of other environmental elements on
EC photolysis in particular environmental settings.
9.6 ENVIRONMENTAL MONITORING OF ECS
9.6.1 Sampling mode and strategy
Sampling plays a crucial role in the monitoring of ECs in wastewater and the environment, as it enables
the collection of representative data. To account for hydraulic retention time (HRT) and assess the
performance of EC removal in treatment processes, relevant grab samples can be utilized. This approach
is particularly suitable for systems like trickling filters, which operate at HRTs of approximately 2 hours
(Petrie etal., 2014). However, for systems such as activated sludge, which commonly have longer HRTs
of 6 h, this method may not be feasible. Additionally, daily grab samples, although commonly collected,
do not provide a comprehensive understanding of the treatment process performance. To ensure
stability and obtain a composite sample representative of a system over a longer period, a sampling
strategy employing flow or volume proportional sampling is necessary. This involves collecting samples
over a period of 24 h, considering the flow rate or volume proportionality (Hillebrand et al., 2013).
Deploying sampling equipment, such as samplers and flow measuring devices, at strategic locations
within WWTPs or rivers presents logistical challenges, but it is essential to obtain representative data
during environmental monitoring. Passive samplers could be a potential alternative, although further
research is needed to assess their suitability for absorbing more polar substances like ECs (Mills etal.,
2014). Ideally, real-time sensors should be employed in situ to enhance monitoring accuracy. The
frequency of repeat sampling efforts throughout the year should also be considered. To capture the
dynamics of seasonal variations, it is recommended to conduct a minimum of two sampling events
per year, representing summer and winter conditions. This approach ensures that the monitoring
reflects the changes that occur throughout different seasons. This will make it possible to determine
the seasonal trends of EC usage and the effect of temperature on the operation of WWTPs. The sample
plan must take into account achieving total mass balances for the concerned WWTP or section of the
river system. Analyzing waste/recycled sludge and river sediment is crucial for figuring out how ECs
behave in these kinds of environments. All sampling positions’ particle phase analyses are part of this.
It is true that obtaining this for final effluents over the course of a thorough sampling program will be
challenging. However, considering the absence of a prior study done here, it is valuable to determine
final effluent particle phase concentrations at least once during the sampling session.
9.6.2 Analysis methods
It is advised to use analytical techniques that can identify ECs down to the enantiomeric level.
However, because chiral stationary phases are so specialized and the mechanism of separation is
poorly understood, establishing multi-residue separations with them is challenging. Additionally,
because of their maximum back pressure, which is typically less than 2000 psi, chiral columns can
only be used in high-performance liquid chromatography mode. Consequently, the ability to process
samples and achieve turnover rates is limited by the commonly observed 60-minute run times (Bagnall
etal., 2012, 2013; López-Serna et al., 2013). To overcome this constraint, it would be advantageous
to utilize stationary phases consisting of smaller particle sizes, specifically below 2 mm. This would
allow for comparable performance in terms of run time and column efficiency to ultraperformance
liquid chromatography (UPLC). Prior to their development, it is advised to ascertain the enantiomeric
fraction for as many substances as feasible using relatively quick achiral UPLC procedures backed by
chiral separations. At relatively quick analytical periods (∼10 min), targeted UPLC approaches can
simultaneously determine up to 100 ECs in distinct environmental matrices (Gracia-Lor etal., 2011;
Gros etal., 2012; López-Serna etal., 2011). These multi-residue methods, which are used to analyze
ECs, should ideally be dynamic so they may carry out targeted (quantitative) determinations while
also doing the non-targeted (qualitative) screening. The use of high-resolution mass spectrometers
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174 Detection and Treatment of Emerging Contaminants in Wastewater
that enable retrospective analysis and can perform both targeted and non-targeted screening, such as
QTOF or Orbitrap technology, is advantageous. With the aid of such technologies, compounds that
were later identified as being of interest but were not initially included in the targeted screening can
be quickly added. A successful chromatographic separation is essential for non-targeted screening.
To separate a wide variety of target ECs exhibiting extremes in physiochemical properties (molecular
weight, hydrophobicity, etc.), the chromatography process needs to be optimized. It will be possible to
find unidentified substances with significant concentrations by combining screening in both negative
and positive ionization modalities. However, due to the unknown behavior of ECs is a big question,
non-targeted screening has a number of drawbacks. They might not thus be retrieved at the time of
sample preparation or during the ionization at the time of analysis. It is also necessary to support
chemical analysis with cutting-edge bioanalytical methods (like metabolomics). At the molecular level,
a metabolomics approach provides valuable insights into the functioning and health of organisms.
Unlike traditional toxicological assays that focus on a limited number of indicator species and
endpoints such as growth, death, and reproduction, metabolomics allows for the detection of detailed
information that would otherwise be overlooked. To comprehensively understand the impact of ECs
and their concentrations on ecological systems, it is essential to conduct lengthy, multigenerational
studies across various trophic levels. These studies should aim to mimic environmental conditions
and replicate EC concentrations observed in the environment. This approach facilitates a better
understanding of how the observed concentrations of ECs in the environment affect the ecology.
9.7 POLICY AND LEGISLATION (INDIA)
Figure 9.2 shows the consumption pattern of different emerging contaminants in India. The National
Environment Policy (NEP) of 2006 represents the most recent manifestation of the government’s
Figure 9.2 Consumption status of pesticides and antibiotics in India (Source: Puri etal. 2023).
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175Tracing the pathways: the journey of emerging contaminants
commitment to enhancing environmental conditions and fostering national economic progress. This
approach empha sizes the int egration of env ironmenta l consideration s into all developme ntal process es,
safeguarding crucial environmental values, and identifying necessary legal and policy adjustments
(Gani & Kazmi, 2016; Richards et al., 2021). Alongside the NEP, the Environment Protection Act
(EPA) was introduced as a comprehensive national environmental law. The EPA outlines measures for
environmental protection in the domains of air, water, and land. It also establishes a framework for
central government coordination with the state authorities established under prior legislation, such as
the Water Act and Air Act (Compliance, 2006).
Currently, Indian sewage treatment facilities discharge their effluents into rivers, traditional
treatment methods are insufficient in eliminating ECs, and adequate waste management practices
are lacking. There is no existing legal legislation specifically addressing ECs in India. The regulations
concerning drinking water in India are only partially covered by the Indian Standards (IS 10500)
(Mathew & Kanmani, 2020).
9.8 CONCLUSIONS AND FUTURE OUTLOOK
Environmental laws are likely to be expanded to include a variety of ECs with municipal origins.
However, there is still a lack of thorough knowledge regarding what happens to them during
wastewater treatment and in the environment. The reported elimination of ECs by W WTP contains
uncertainty because of the shortcomings of the current sampling techniques. Therefore, it is necessary
to reevaluate, using appropriate sample techniques, the removal efficacy of various WWTP process
types under varying operational situations. This will make it easier to determine the steps needed for
EC improvement. The use of novel treatment techniques will rise in response to the growing trend of
enhancing sustainability and decreasing energy consumption for wastewater treatment. An example
of a promising treatment approach that can inadvertently generate energy is the use of algal ponds for
secondary effluent polishing. However, very few studies have kept track of how well they perform in
terms of removing EC. To assess the fate and removal of ECs during treatment, taking into account
their probable integration into the standard WWTPs flow sheet, additional research on these process
types is required. Now, environmental monitoring must adopt a comprehensive strategy. This entails
figuring out what happens to ECs and how they affect the environment over their whole life cycle,
which includes the terrestrial environment. In-depth case studies of supplemented soils in real-world
settings are required to examine leaching, runoff, the effect on the quality of nearby surface waters,
soil deterioration, the toxicity to terrestrial creatures, and potential uptake by plants and entry into
the human food chain. Monitoring other contaminated environmental compartments, such as river
sediments, can be done using a similar strategy. Finally, the revision and creation of a more accurate
environmental risk assessment will be made possible by the combined use of chemical and biological
studies to better analyze the environmental impact of ECs.
ACKNOWLEDGMENTS
Director, CSIR-NEERI is thankfully acknowledged for giving the opportunity to pursue work in
CSIR-NEERI, Nagpur, India. AS and CJ acknowledge the University Grant Commission, New Delhi,
India for providing Senior and Junior Research Fellowship. The article is checked for plagiarism using
the iThenticate software and recorded in the Knowledge Resource Center, CSIR-NEERI, Nagpur for
anti-plagiarism.
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Wang Y., Westerhoff P. and Hristovski K. D. (2012). Fate and biological effects of silver, titanium dioxide, and
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West C. E. and Rowland S. J. (2012). Aqueous phototransformation of diazepam and related human metabolites under
simulated sunlight. Environmental Science & Technology, 46, 4749–4756, https://doi.org/10.1021/es203529z
Wilson M. and Ashra f M. A. (2018). Study of fate and transport of emergent contaminants at waste water treatment
plant. Environmental Contaminants Reviews, 1, 01–12, https://doi.org/10.26480/ecr.01.2018.01.12
Yang G. C., Yen C.-H. and Wang C.-L. (2014). Monitoring and removal of residual phthalate esters and
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53– 61, https://doi.org/10.1016/j.jhazmat.2014.03.005
Yang X., Hu Z., Liu Y., Xie X., Huang L., Zhang R. and Dong B. (2022). Effect of pyrene-induced changes in
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in sewage treatment plants. Water Research, 43, 2399–2408, https://doi.org/10.1016/j.watres.2009.03.009
Zhou H., Wu C. , Huang X., Gao M ., Wen X. , Tsuno H. and Tanak a H. (2010). Occurren ce of selected pha rmaceu ticals
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© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0181
Akanksha Bakshi, Megha Latwal, Sonali, Nitika Sharma, Anamika Sharma,
Jatinder Kaur Katnoria and Avinash Kaur Nagpal*
Department of Botanical and Environmental Sciences, Guru Nanak Dev University, Amritsar, Punjab 143005, India
*Corresponding author: avinash.botenv@gndu.ac.in
ABSTRACT
Nowadays, pharmaceuticals and personal care products (PPCPs) are being used by almost every section of
society and are classified as ‘emerging pollutants’ due to their adverse effects on human and environmental
health. They consist of different chemical compounds, hormones, and human and veterinarian prescription drugs.
These are discharged into wastewater and find their way to aquatic ecosystems and even drinking water. A rising
environmental problem is the presence of pharmaceuticals, hormones, and personal care products in sources
of drinking and surface water. These substances have been identified in samples of surface water, groundwater
and even drinking water in quantities ranging from parts-per-trillion (ng/L) to parts-per-billion (µg/L). Traditional
sewage treatment plants and industrial wastewater treatment plants (WWTPs) can get rid of common pollutants
like pathogens, nutrients, and organic matter but they fail to remove PPCPs which causes them to be released into
the aquatic environment. Individual PPCPs can be successfully removed using a variety of treatment methods, such
as membrane filtering, granular activated carbon, and advanced oxidation procedures. The use of a membrane
bioreactor might also be an attractive means for dealing with pharmaceuticals. Due to their negative impacts on the
ecosystem, information on their fate and interaction is essential for their management. Therefore, the present study
focuses on the sources, types, effects, monitoring and suitable removal techniques for different PPCPs.
10.1 INTRODUCTION
Pharmaceutical and personal care products, abbreviated as PPCPs, are a group of numerous
compounds or chemicals that include veterinary and human medication, nutraceuticals, bioactive food
supplements, and common household goods such as soaps, shampoos, toothpaste, cosmetic products
and so on. Despite their numerous advantages, these compounds are expected to pose potentially
hazardous side effects. These chemical compounds are typically released either directly or indirectly
into wastewater systems and have a negative impact on the environment (Kumar et al., 2023). The
occurrence of PPCPs in wastewater systems has recently attracted significant global attention and
has become a topic of growing concern as they affect both human health and ecosystems. Unlike
conventional pollutants, PPCPs can have specific biological effects, and their presence in water bodies
Chapter 10
Fate and behaviour of pharmaceutical
and personal care products in
wastewater
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182 Detection and Treatment of Emerging Contaminants in Wastewater
can lead to unintended consequences. Some PPCP compounds remain unnoticed in the environment
and unregulated. United States Environmental Protection Agency has listed some of these
unmonitored PPCPs as priority pollutants (Anand etal., 2022). Among the various PPCP sources,
wastewater treatment plants (WWTPs) are primarily responsible for the presence of these chemicals
in the ecosystem (Silori & Tauseef, 2022). Traditional wastewater treatment facilities like membrane
filtration, advanced oxidation and adsorption are primarily employed to get rid of common pollutants
like nutrients, organic matter and pathogens. However, they often fail to remove PPCPs, which causes
them to be released into aquatic system (Kumar et al., 2022). This results in the contamination of
the majority of aquatic ecosystems. Once ingested, these PPCPs have the potential to disrupt the
endocrine system and increase the risk of developing antimicrobial resistance, which results in the
loss of the effectiveness of the majority of common antibiotics (Kumar et a l., 2022). Hence, there
is an urgency to regulate the PPCP concentrations in different water bodies like wastewater and
drinkable water. Prior to being disposed of into the environment, these substances must first undergo
proper treatment. When PPCPs enter wastewater systems, complicated processes determine their
fate and behaviour including their transformation, environmental effects, persistence and movement.
Some countries have already started the treatment of wastewater containing PPCPs in their sewage
treatment plants (STPs) and wastewater treatment plants (WWTPs) via sorption or biodegradation
(Guerrero-Gualan et al., 2023). They can also undergo chemical changes via conjugate cleavage or
pass through the system without any change. The concentration of PPCPs following treatment could
go down, up, or stay same as untreated sewage (Agnihotri & Thathola, 2019).
For the purpose of removing PPCPs from water bodies, a number of different processes have
already been covered by many reviewers, including adsorption, ozonation, UV oxidation, membrane
filtration, biological processes, and Fenton oxidation (John et al., 2022; Kumar et al., 2022;
Zhang etal., 2022). Other than these, constructed wetlands (CWs) are also used to remove these
chemicals from the water bodies. CWs are considered as most sustainable and environmentally
friendly method used to remove different PPCPs. In CWs, macrophytes and associated microbial
assemblages effectively degrade/transform various PPCPs (Kumar etal., 2023). Treatment plants are
not completely capable of eliminating or neutralizing these PPCPs and regulatory effluent standards
do not include any PPCP concentration parameters, hence their release into the environment
remains unchecked and unmonitored (Bavumiragira & Yin, 2022). In addition, some PPCPs have
the potential to transform into metabolites or other secondary products with potentially different
properties and increased environmental risks. PPCP removal effectiveness of various processes
depends on the reaction mechanism and PPCPs’ chemical structures. Due to the wide range of
chemical and physical properties of PPCPs, none of these processes can completely eliminate them.
However, their combined effects may make it easier to get rid of these PPCPs from the water system
(Loganathan etal., 2023).
Understanding the fate and behaviour of PPCPs in wastewater is critical for developing effective
mitigation strategies. To do this, it is necessary to examine their occurrence and concentration in
wastewater influents, effluents, and sludge as well as their behaviour throughout various wastewater
treatment processes. Additionally, identification of transformation products and their potential
toxicity is crucial for assessing the overall environmental risk associated with PPCPs (Liu et al.,
2020). This chapter represents a significant advancement over prior literature as it incorporates the
latest research, advanced methodologies as well as provides a comprehensive overview of the fate
and behaviour of PPCPs in wastewater, highlighting the challenges and potential solutions for their
removal and mitigation. By improving our understanding of the behaviour and potential risks of
these emerging contaminants, we can work towards developing more efficient treatment technologies
and implementing appropriate regulatory measures to safeguard water resources and protect both
human and ecological health. Fig ure 10.1 shows various sources of PPCPs and their pathway in
environment.
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183Fate and behaviour of pharmaceutical and personal care products in wastewater
10.2 MAJOR CATEGORIES OF PPCPS
In 2005, the European Union (EU) initiated the ‘Norman Project’ to monitor the emerging pollutants
being reported around the world and found more than 1036 contaminants and their products which
were classified into 30 categories. PPCPs were classified as a major category of emerging pollutants
(Ricky & Shanthakumar, 2022). As a consequence of increasing utilization of PPCPs, more of these
products are being released into wastewater through wash-off, urine, and feces as parent compounds,
conjugates or their derivatives (Bavumiragira & Yin, 2022). Major categories of PPCPs are presented
in Figure 10.2. In the following two sub-sections, categories of pharmaceutical products and personal
care products are being discussed separately.
10.2.1 Categories of pharmaceutical products
Pharmaceutical products consist of active ingredients (chemically manufactured or natural
substances) present in prescription and non-prescription drugs, veterinary medications, and illegal
drugs. These include antibiotics, stimulants, hormones and steroids, non-steroidal anti-inflammatory
drugs (NSAIDs), antihypertensives, lipid regulators and antidepressants.
Antibiotics are utilized for curing infections caused by bacteria in humans and animals and are
passed out from body either in metabolized or unmetabolized forms (Sodhi etal., 2021). Even after
excretion, they do not get fully degraded in the environment and persist in water bodies. Some of the
antibiotics that have been reported in wastewaters worldwide include erythromycin from Croatia
Figure 10.1 Schematic diagram showing various PPCP sources and their pathways in the environment. *STPs –
sewage treatment plants; WWTPs – wastewater treatment plants.
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184 Detection and Treatment of Emerging Contaminants in Wastewater
(Senta et al., 2019); ciprofloxacin and ofloxacin from Spain (Bijlsma etal., 2021); and tetracycline from
Beijing (Zhang etal., 2018).
Caffe ine, 1,3,7-trime thylxant hine, is t he oldest known st imulant wh ich is a natura l alkaloid belon ging
to the family of xanthines. Its structure is similar to adenosine and impedes its activity by acting on
its receptors (Cerveny e t al., 2022). Adenosine has a crucial role in sleep–wake cycle, locomotive
and psychological activities. As a pharmaceutical, caffeine is used to prevent sleepiness, treat pain,
circulatory system failure and respiratory issues. It is the most commonly detected contaminant in
wastewater because of its high consumption and presence in chocolates and beverages such as tea,
coffee, sodas, and so on. Its presence in water is considered as an indicator of water pollution caused
due to human activities ( Júnior etal., 2019).
Hormones are used to maintain physical growth and sexual wellness in organisms (Wang & Wang,
2016). Utilization of steroids and hormones in livestock agriculture has emerged as a major problem
since they contaminate the water resources. Steroids and hormones, which are frequently found in
WWTPs, include androgens, estrogens, progestogens, and growth hormones (Guerrero-Gualan etal.,
Figure 10.2 Major categories of PPCPs.
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185Fate and behaviour of pharmaceutical and personal care products in wastewater
2023). Estrogens are the most commonly reported hormones in sewage, wastewater, and surface water
(Damkjaer etal., 2018; Yazda n etal., 2022).
Non-steroidal anti-inflammatory drugs (NSAIDs) are among the commonly used drugs to
alleviate pain and inflammation in patients suffering from arthritis, menstrual cramps, postoperative
conditions, and so on. Among different types of NSAIDs, diclofenac, naproxen, ketoprofen, and
ibuprofen are the most common drugs detected in aquatic systems (Mussa etal., 2022). Due to their
toxicity and persistence, European Union (EU) regards NSAIDs as high priority pharmaceuticals
(Rastogi etal., 2021). NSAIDs have been reported from different WWTPs like WWTPs of Durban,
South Africa (Madikizela & Chimuka, 2017); and WWTPs of Mangalore, India (Thalla & Vannarath,
2020). Besides parent compounds, metabolites of NSAIDs have also been reported in different waste
and surface waters (Březinova etal., 2018).
Two main lipid regulators used to control the levels of triglycerides and cholesterol in blood are
fibrates and statins. Fibrates function by lowering the levels of fatty acids and triglycerides whereas
statins decrease cholesterol level. Fibrates are the derivatives of fibric acid. Clofibric acid is a
persistent compound that is detected in water years after its emission (Rosal etal., 2010). It is also the
most commonly reported drug among fibrates in water. Commonly used statins worldwide include
atorvastatin, lovastatin, pitavastatin, pravastatin, simvastatin and fluvastatin (Blonç et al., 2023).
Compounds such as bezafibrate, clofibrate, gemfibrozil, atorvastatin and simvastatin are the most
prevalent pharmaceuticals in water systems (Ulvi etal., 2022). Ramírez-Morales etal . (2020) reported
presence of gemfibrozil in wastewater samples from 11 WWTPs in Costa Rica. Lipid regulators have
also been reported from wastewaters of Mahdia, Tunisia (Afsa et al., 2020); Sri Lanka (Goswami
etal., 2022); and Jiangsu Province, China (Liu etal., 2023).
Antihypertensives dr ugs used for the treatment of high blood pressure which is the common cause of
cardiovascular diseases (Subedi etal ., 2017). These include angiotensin converting enzyme inhibitors,
diuretics, β-blockers (blockers of β-adrenergic receptors), angiotensin II receptor antagonists and
calcium channel blockers. Increase in their concentration in water systems stems from increase in the
number of patients with cardiovascular diseases. Reuse of treated wastewater in agricultural fields
often leads to addition of these pollutants to soil affecting soil microbes and organisms. Presence of
antihypertensives has been reported from six STPs in Bavaria (Bayer et al., 2014); two WWTPs of
Albany, New York (Subedi and Kannan, 2015); three WWTPs from Foshan and Guangzhou, China
(Huang etal., 2018); and WWTPs of two major cities of Colombia (Botero-Coy etal., 2018).
Antidepressants regulate mood by targeting specific neurotransmitters. On the basis of their mode
of action, they can be classified as tricyclic antidepressants (TCA) for example amoxapine; selective
serotonin reuptake inhibitors (SSRIs) for example citalopram; selective noradrenaline reuptake
inhibitors (NARI) for example amedalin; serotonin-norepinephrine reuptake inhibitors (SNRIs) for
example duloxetine; and monoamine oxidase inhibitors (MAOIs) for example isocarboxazid (Chen
et al., 2022). Occurrence of antidepressants has been reported from two WWTPs of Albany, New
Yor k (Subedi & Kannan, 2015); two municipal W WTPs and Rhine River in Germany (Schlüsener
et al., 2015); and municipal WWTPs of Tehran, Iran (Golbaz etal., 2023). High concentrations of
venlafaxine have been reported from two WWTPs in Greece (Ofrydopoulou etal., 2022). In China
also, venlafaxine and its metabolite were found in WWTPs at Shanghai (Ma etal., 2018).
10.2.2 Categories of personal care products (PCPs)
PCPs are a large group of compounds including both inert as well as active ingredients used for
personal care and hygiene (Figure 10.2). PCPs mainly include dyes, make-up products, oral hygiene
products, preservatives, disinfectants, fragrances, sunlight UV filters, food additives, supplements, and
insect repellents (Ricky & Shanthakumar 2022). PCPs, now considered as emerging contaminants,
have been detected in trace concentrations (ranging from ng/L to mg/L) in industrial wastewater as
well as sewage and sludges (Anand et al., 2022), and different ground and surface waters (Cooney
et al., 2023; Nozaki etal., 2023). They are thought to escape STPs and WWTPs (in their original
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186 Detection and Treatment of Emerging Contaminants in Wastewater
or biologically altered forms) and make their way to both surface and groundwater systems causing
environmental contamination (Anand et al., 2022). Active constituents of common personal care
products are given in Table 10.1.
Fragrances (compounds with sweet odour) are important constituents of perfumes, deodorants,
shampoos, conditioners, and many cleaning products used in everyday life. Different kinds of musk
fragrances (aromatic compounds) are used in the perfume industry. Natural musk is obtained from
animals, particularly from male musk deer or from a cat with a musk civet. Nitro musks (musk xylene
and musk ketone) and polycyclic musks (Galaxolide HHCB and tonalide ATHN) come under synthetic
musks. HHCB is the most widely used synthetic musk recognized as an emerging contaminant and
affects human health (Li et al., 2021). Other musks include macrocyclic musks and alicyclic musks.
Tasselli and Guzzella (2020) detected galaxolide and its metabolite galaxolidone in the sludge of a
WWTP in Northern Italy. Tasselli et al. (2021) investigated the presence of PCPs (HHCB, AHTN,
celestolide, etc.) in municipal and industrial sludge and wastewater in Milan, Northern Italy.
Galaxolide, tonalide, musk xylene, and musk ketone were found in abundance from sewage sludge
samples collected in 55 WWTPs in the Czech Republic (Košnář etal., 2021).
Sunscreen products contain various chemicals which act as protectants against UV radiation.
Commonly known as UV filters, they are effective against harmful UV rays and are divided into two
categories viz. organic filters and inorganic filters. Organic filters include benzophenone 3 (BP-3),
2-ethylhexyl 4-methoxycinnamate (octinoxate, EHMC), oxybenzone, avobenzone, and inorganic ones
Table 10.1 Active constituents of common PCPs.
Fragrances Sunscreens Insect
Repellents
Disinfectants Preservatives and
Additives
Nitro musks
Musk ambrette
Musk alpha
Musk ketone
Musk moskene
Musk tibetene
Polycyclic musks
Celestolide
Fixolide
Galaxolide
Traseolide
Ver salide
Alicyclic musks
Cyclomusk
Helvetolide
Romandolide
Macrocyclic musks
Ambrettolide
Cyclopentadecanolide
Ethylene brassilate
Globalide
Velvione
Benzophenone-3
(BP-3)
4-methyl-benzylidene
camphor (4- MBC)
Octocrylene (OC)
2-ethyl-hexyl-4- tri
methoxycinnamate
(EHMC)
Oxybenzone
N,N-diethyl-
m-toluamide
(DEET)
Benzyl dimethyl
dodecyl ammonium
chloride
Dioctyl dimethyl
ammonium chloride
Ethanol
Methylparaben
2-phenyl phenol
Isopropanol
Triclosan
Benzyl acetate.
Bronidox
Iodopropynyl butyl
carbamate (IPBC)
Propylparaben
Sucralose
2,4,4-trichloro-2
-hydroxy diphenyl
ether
Agnihotri and
Thathola (2019)
Agnihotri and
Thathola (2019);
Ricky and
Shanthakumar
(2022)
Merel and
Snyder
(2016)
Al-Baldawi etal.
(2021); Ricky and
Shanthakumar
(2022)
Al-Baldawi etal.
(2021)
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187Fate and behaviour of pharmaceutical and personal care products in wastewater
including zinc oxide (ZnO) and tit anium dioxide ( TiO2) (Tsui et a l ., 2014). (BP-3), 4-methyl benzylidene
camphor (4-MBC), and EHMC are the most common UV filters found in daily activity products such
as cosmetics (Tran et al., 2022). In an earlier study, BP3 was detected from WWTP influents from
southern California (USA) with a concentration of 10 µg/l (Mao etal., 2019). Benzophenones (BPs)
were detected in water samples from Huangpu River, China (Wang etal., 2021). Tran etal. (2022)
reported BP-3 and BP-4 to be the most common UV filters found in wastewater. Hsieh etal. (2023)
detected triclosan and BP-3 from three WWTPs in southern Taiwan.
Insect repellents are the most commonly detected contaminants in water samples. N N-diethyl-
m-toluamide (DEET), an insect repellent and was developed by the US Army in 1946 (Kitchen etal.,
2009). DEET and its products are potential toxicants, which is a matter of concern with regard to
human health and the environment (Xu etal., 2022). Merel and Snyder (2016) reviewed the literature
on the occurrence and fate of DEET in water across the globe. The study concluded that DEET had
been detected in almost all types of aquatic ecosystems including ground and surface waters as well
as wastewaters from different parts of the globe including America, Asia, Africa, Europe and Oceania.
Güzel (2021) detected DEET in the Seyhan River (Turkey) and its concentration was relatively higher
in autumn than in summer.
Disinfectants are used for surface cleaning, instrument disinfection and so on. Alcohol, aldehydes
and chlorine-containing compounds are the main active ingredients. Methylparaben, 2-phenyl
phenol, triclosan and alcohols (isopropanol and ethanol) are the most commonly used chemicals
as disinfectants. The concentrations of these compounds in urban runoff and groundwater have
increased significantly in recent years (Rodriguez-Narvaez e t al., 2017). One of the most popular
biocides is triclosan (TRC), which is detected in aquatic environments at high rates.
Preservatives are used in PCPs mainly cosmetics, food, and beverages as they protect these
products against microbial growth. Table 10.1 gives the active constituents of preservatives. Triclosan
and triclocarban are prime active ingredients widely used in personal hygiene products (Musee, 2018).
Due to the insufficient removal from WWTPs, cosmetic preservatives have been widely detected in
aquatic environments and sewage sludge. Parabens are the most extensively used preservatives in
PCPs due to their high stability (Penrose & Cobb, 2023).
10.3 OCCURRENCE OF PPCPS IN WATER ECOSYSTEM
PPCPs though enter surface waters at low doses, but long-term exposure has the potential to harm
aquatic organisms. Several studies carried out around the globe have shown PPCP contamination
of surface water. Liu et al. (2020) reported the presence of 50 PPCPs in the Chinese aquatic system
in concentrations between ng/L and g/L. Bisognin etal. (2021) demonstrated presence of 13 PPCPs
including paracetamol, caffeine, metronidazole and sulphamethoxazole in the effluent and sludge
samples from STPs in southern Brazil. Nozaki e t al. (2023) found 43 PPCPs including triclosan,
triclocarban, chlorpheniramine, diphenhydramine, and chlorpheniramine in freshwater samples
from different rivers, lakes and/or ponds from three Asian countries viz. India, Indonesia and
Vietnam. Balakrishna etal. (2017) reviewed studies from India that showed the presence of PPCPs
like atenolol, triclosan, carbamazepine, trimethoprim, ibuprofen, acetaminophen, caffeine and
triclocarban in different rivers. Sharma etal. (2019) reported occurrence of 15 PPCPs in the Ganga
River and groundwater of several sites along the river. Out of 15 PPCPs, caffeine was found to be most
prevalent. Singh and Suthar (2021) showed the occurrence of different PPCPs like triclosan, caffeine,
acetaminophen and tetracycline in Ganga River at Rishikesh and Haridwar cities. Yu etal. (2023)
detected the presence of artificial sweeteners in Yellow River of China. Okoye etal. (2022) reported
the occurrence of PPCPs in surface waters of Africa.
Groundwater is a critical water source with significant environmental concerns as it provides
water for human consumption, ecosystem demands and irrigation. Different concentrations of
various PPCPs have been found to contaminate groundwater. In a recent study, different antibiotics
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188 Detection and Treatment of Emerging Contaminants in Wastewater
like erythromycin, trimethoprim, clindamycin and ofloxacin were detected in the groundwater of
the Bialka River valley in Poland (Lenart-Boroń et al., 2022). Cooney etal. (2023) also noted high
concentrations of antibiotics such as cephalexin, ampicillin, sulphamethoxazole, trimethoprim,
tetracyclin, oxytetracycline and erythromycin in groundwater of Riviera Maya, Mexico. Caffeine has
been found in many groundwater samples from all over the world and enters into the water system
through various household activities and human urine. The presence of caffeine has been shown in
various effluents, landfills, septic tanks and wastewater that can contaminate the groundwater by
natural recycling process (Cerveny etal., 2022; Do etal., 2022; Júnior etal., 2019; Sui etal., 2015). As
compared to other PPCPs, consumption of caffeine is much higher in day-to-day life and is expected
to be present in higher concentrations in groundwater. However, Sui etal. (2015) observed that the
concentration of caffeine in groundwater was not higher as compared to other PPCPs. It is expected
that caffeine might either be removed during wastewater treatment or it can undergo degradation
rapidly. Do etal. (2022) noted that 80% of groundwater of Hawpe village in Sri Lanka’s Galle district
was contaminated with caffeine (7.9 ng/L).
Lipid regulators like bezafibrate, clofibric acid and gemfibrozil have been detected in groundwater,
however, their concentration was negligible as compared to other PPCPs like anti-inflammatories,
antibiotics, caffeine and so on (Sui etal., 2015; Wang & Wang, 2016). Clofibric acid and gemfibrozil
were detected at lower concentrations in groundwater samples from China, Spain and Singapore
(López-Serna etal., 2013; Peng etal., 2 014; Tran etal., 2014). Some lipid regulators were also found
in the groundwater of Barcelona, Spain which included bezafibrate (López-Serna etal., 2013) and
clofibric acid (Jurado etal., 2022). Gemfibrozil has been observed in waterbodies of Marmara, Turkey
(Korkmaz et al., 2022) and in the surface water of the Beijiang River and surrounding groundwater
(Lei etal., 2023).
Some studies have shown the presence of some PPCPs including X-ray film contrast media, musks,
sunscreen agents and beta blockers in groundwater (Subedi et al., 2 017). Zemann et al. (2015)
reported the presence of iodinated X-ray contrast media (ICM) in the groundwater of Wadi Shueib,
Jordan. However, groundwater samples from Barcelona, Spain were mainly contaminated with
tonalide, octocrylene, ethylhexyl methoxycinnamate, propranolol, metoprolol and musk galaxolide
(Jurado etal., 2022; López-Serna etal., 2013). In a groundwater sample from Riviera Maya, Mexico,
sunscreens were found (Cooney etal ., 2023). Other PPCPS like acetaminophen, climbazole, cotinine,
carbamazepine, crotamiton, atenolol and lidocaine were also detected in groundwater samples of
Spain (Jurado etal., 2022); Poland (Lenart-Boroń etal., 2022); and Sri Lanka (Do etal., 2022).
PPCPs were also found in the effluents from both sewage and wastewater treatment plants due to
their extensive use and incomplete removal during the treatment process. Industrial setups produce
huge quantities of wastewater. Solid wastes of these PPCPs are generally discarded into landfills and
garbage sites. Likewise, effluents of wastewater treatment plants and biosolids produced from sludges
also contain large amount of PPCPs which ultimately contaminate agricultural lands (Anand etal.,
2022). Conventional wastewater treatment processes are not designed to specifically remove PPCPs,
resulting in incomplete removal of these compounds during treatment. PPCPs can persist in the
effluent and are often discharged into receiving waters (Anand etal., 2022; Guerrero-Gualan etal.,
2023; Kumar etal., 2022). Different PPCPs, including ranitidine hydrochloride, sulphamethoxazole,
ibuprofen, ampicillin sodium, ribavirin, and clozapine, have been found in the effluent of Chinese
WWTPs (Liu etal., 2022). Similarly, Kumar etal. (2023) found Ibuprofen, 1-hexadecanoyl-sn-glycerol
(1HSG), acetaminophen, triclocarban, trimethoprim, 19-docosapentaynoic acid, sulphamethoxazole,
arbamazepine and caffeine in wastewater effluent of an academic institution of Gandhinagar, Gujrat.
Concentrations of PPCPs can range from low (parts per billion (ppb)) to high (parts per million
(ppm)) levels (Ebele et al., 2020). The occurrence and concentrations of PPCPs in effluents from
STPs and WWTPs can vary depending on several factors including population density, wastewater
characteristics, and local usage patterns.
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189Fate and behaviour of pharmaceutical and personal care products in wastewater
10.4 SOURCES AND FATE OF PPCPS
10.4.1 Sources of PPCPs in wastewater
Anthropogenic activities are the main sources of PPCPs in the environment (Al-Baldawi etal., 2021).
The emission of PPCPs in wastewater starts from t he manufacturing of pharmaceutical ingredients and
PCPs by industries proceeding with the utilization of these products by hospitals, households, animal
husbandry, fish rearing and so on (Falahi etal., 2022). Healthcare institutions are important sources
of pharmaceutical discard (Anand et al., 2022). The unmetabolized products of the pharmaceutical
drugs used by patients in hospitals, households and so on are excreted and discharged into wastewater/
STPs (Al-Baldawi etal., 2021). Veterinary pharmaceuticals used by animal husbandry and aquaculture
practices are also responsible for polluting water and soil. Animal excreta containing unmetabolized
drugs is released directly into surface waters or converted into manure and applied in fields where
it can contaminate the groundwater (Ebele et al ., 2020). Alternatively, personal care products are
used more extensively and frequently, hence, producing more quantities of waste. These products are
discharged from homes into wastewater treatment facilities whereas, households without the facility
directly discharge their wastewater into surface water systems such as rivers and streams (Wang &
Wang, 2016). Personal care products are lipophilic by nature and adsorb onto sediments (Okoye eta l.,
2022). Another prevalent practice is dumping expired PPCPs in solid waste which leads to leaching of
these contaminants in soil and groundwater. In urban areas, due to a more organized sewage system,
PPCP-contaminated wastewater from different sources accumulated in STPs. Since these systems
cannot treat PPCP-laden wastewater, these contaminants get discharged into water bodies.
10.4.2 Fate of PPCPs in wastewater
PPCPs present direct and indirect effects on the environment such as the development of bacterial
resistance, disturbance of the endocrine system and bioaccumulation in organisms (Nozaki et a l.,
2023). They are classified as pseudo-persistent contaminants due to their polarity, optical activity
and semi-volatility (Liu et al., 2022). Personal care products are mainly used on hair and skin and
are discharged (by excretion and washing) into wastewater (Anand etal., 2022). They may further
degrade by coming in contact with sunlight (UV radiations), air (oxidation), water, microbes and
so on (Anand et a l., 2022). As degradation of PPCPs is dependent on their chemical and physical
composition, different products will degrade in different proportions. Compounds such as caffeine
and paracetamol are widely used but often detected in less quantities due to more biodegradation as
compared to carbamazepine and sulphamethoxazole which are persistent (Sui etal., 2015). Due to the
absence of treatment techniques for these compounds, most of the treated wastewaters contain PPCPs
in the undegraded form which are released into water bodies. When they are continuously released in
water bodies, the non-target species bioaccumulate these contaminants over time and pass them into
the food chain (biomagnification). Many PPCPs such as ciprofloxacin and galaxolide have been found
to be bioaccumulated in aquatic species. The presence of antibacterial compounds has been observed
to develop antibiotic resistance in non-target microorganisms (Ricky & Shanthakumar, 2022).
10.5 HARMFUL EFFECTS OF PPCPS
The continuous release of PPCPs into bodies of water, as well as their exposure, may have chronic
consequences on aquatic plants and animals (Silori & Tauseef, 2022). The presence of PPCPs in water
systems causes genotoxicity, mutagenesis, and ecotoxicity in plants, animals, and humans.
PPCPs reach plants largely through irrigation with recovered wastewater, application of manure
and biosolids for agricultural soil fertilization and deposition from volatilized chemicals. PPCPs are
absorbed by plants through their aerial tissues and roots by the process of mass flow or diffusion
of dissolved compounds. Deposition of vaporized compounds and aerosols, direct contact with
irrigation or amendment materials, and translocation from root tissues are all ways for aerial
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190 Detection and Treatment of Emerging Contaminants in Wastewater
tissues to absorb (Trapp & Legind, 2011). In an experiment conducted by Pérez etal. (2023), Typha
latifolia was exposed to some PPCPs viz. triclosan, gemfibrozil, carbamazepine and fluoxetine and
it was observed that triclosan and gemfibrozil were accumulated in roots while carbamazepine and
fluoxetine accumulated in leaf tissues. Zeng etal. (2022) reported accumulation of PPCPs including
amant adine, ca rbamazepine ch lorphenira mine, chlorosi butrami ne haemosibutra mine, N-monomet hyl
sibutramine, and sibutramine in radish, buckwheat and okra (sprouting seeds). Falahi et al. (2022)
reported the accumulation of Ibuprofen and paracetamol in the roots and shoots of Scirpus grossus.
PPCPs accumulated by plants can be metabolized, detoxified, inactivated, and sequestered by the
plant’s defence mechanism and thus it appears that the majority of PPCPs do not cause phytotoxicity.
However, some recent studies have shown that prolonged exposure of plants to PPCPs leads to the
overproduction of ROS that is, oxidative damage (Sun etal., 2018). Osma etal. (2018) reported that
two PPCPs viz. ß-estradiol and gemfibrozil produced a negative effect on wheat seedlings through
oxidative stress. Ravichandran and Philip (2022) noted that the deposition of carbamazepine (anti-
epileptic drug) on four wetland plants (Canna indica, Chrysopogon zizanioides, Colocasia esculenta
and Phragmites australis) led to oxidative stress in these plants. Similarly, Elveren and Osma (2022)
reported an increase in the activity of catalase, peroxidase and superoxide dismutase in Triticum
aestivum (L.) on exposure to PPCPs like ciprofloxacin, doxylamine succinate, and ibuprofen.
The presence of PPCPs in aquatic systems has been shown to have deleterious effects on aquatic
organisms. In a recent study by Chabchoubi et al. (2023), NSAIDS like Ibuprofen, diclofenac,
paracetamol and ketoprofen were found to adversely affect the embryo and larval growth of a
Zebrafish, Danio rerio. In another study, indomethacin, ibuprofen and their mixture were observed
to affect the rate of food intake and enzymatic activities in a crustacean, Daphnia magna (Michalaki
& Grintzalis, 2023). Cory et al. (2019) reported toxicity of naproxen and its photo-transformation
derivatives (NAP-PT1 and NAP-PT2) in Anaxyrus terrestris larvae. Diclofenac and its metabolite
4-hydroxydiclofenac were shown to cause deformations and low protein content in the gills of a
mollusc, Mytilus trossulus (Świacka et al., 2022). Liu et al. (2018) documented the toxicology of
antibiotic pollution in many aquatic organisms such as tetrogenic effects of macrolides, tetracyclines,
sulphonamides, quinolones and so on on aquatic vertebrates such as Danio rerio and Xenopus
tropicalis and toxicity of quinolone antibiotics in tilapia, Oreochronis niloticus. Reckless consumption
of antibiotics is also one of the major reasons for the increase in the emergence of antibiotic-resistant
genes (ARGs) (Langbehn etal., 2021).
Various studies have shown the ability of hormones present in wastewater to cause endocrine
disruption in aquatic species. Bahamonde etal. (2015) reported intersex conditions in male fishes
(Etheostoma caeruleum) exposed to municipal wastewater effluent in Grand River, Canada. Plahuta
et al. (2017) showed the potential of influent and effluent wastewater containing EDCs (estrogens)
to hamper the moulting ability of Asellus aquaticus. Leese et al. (2021) observed changes in the
reproductive behaviour of fathead minnows on exposure to EDC containing wastewater effluent.
Estrogen and testosterone levels in a fish species, Oryzias latipes, were disturbed on exposure to a
lipid-regulating medication-gemfibrozil (Lee etal., 2019). Whereas in another study, the presence of
gemfibrozil in water affected antioxidant enzymes activity in liver of Danio rerio (Falfushynska etal.,
2022). The presence of antihypertensives in water is also shown to have deleterious effects on aquatic
animals (Pusceddu etal., 2022). The presence of antidepressants in the sewage water has been shown
to affect the behaviour of aquatic species. Antonopoulou etal. (2022) reported toxicity of Paroxetine,
an antidepressant, on freshwater and marine species, bacteria and human lymphocytes.
Antiepileptic drugs (AEDs) are frequently present in various aquatic ecosystems, making aquatic
organisms vulnerable to these medications. Salahinejad etal. (2023) reviewed literature on effect of
some antiepileptic drugs on teleost fishes. It was concluded that AEDs disrupted parasympathetic
neurotransmitters, and serotonergic and glutamatergic systems in fishes. Gebuij’s etal. (2020) studied
the concentration dependent effect of an antiepileptic drug (valproic acid) on the survivability of
Zebra fish. It was found that the drug exposure led to decrease in bone and cartilage development,
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191Fate and behaviour of pharmaceutical and personal care products in wastewater
and reduction in the length of the ethmoid plate. Organic UV filters are found to be extensively
accumulated in aquatic organisms and are known to impact the survivability, development and
reproduction of aquatic organisms. Zhou et al. (2019) investigated the effect of organic UV filter
(OUVF), ethylhexyl methoxy cinnamate (EHMC), on the growth and reproduction of Danio rerio
(Zebra fish) and the study revealed that EHMC caused a reduction in the number of hatchlings and
increase in mortality rate of Danio rerio embryo. In another study done was by Zhou etal. (2020),
OUVFs 4-methyl benzylidene camphor (4-MBC) and sulphanilamide antibiotic, sulphamethoxazole
caused slow growth, body weight reduction, impaired vitality and irregular behaviour of Danio rerio.
PPCPs in the environment around the world have been linked to negative impacts on human
health. Generally, PPCPs enter the human body by drinking water or the ingestion of vegetables,
fruits and crops irrigated with contaminated water. NSAIDs, commonly used for treatment of
musculoskeletal pain, have direct side-effects on human health such as cardiovascular problems
(heart attacks, hypertension), gastrointestinal issues (ulcers, perforation, bleeding) and kidney-related
problems (Banerjee & Maric, 2023; Machado et al., 2021). Overconsumption of antibiotics leads to
antibiotic-resistant bacteria and antibiotic-resistant genes, posing a great threat to the human health
by increasing the chances of infections and difficulty in treating them (Seethalakshmi et al., 2022).
EDCs have been shown to affect the synthesis and action of sex steroid hormones which in turn
leads to hormone sensitive cancers and infertility in men and women (Yilmaz etal., 2020). Caffeine
besides being one of the best-known stimulants, has been linked to many health issues when taken in
higher doses. (Tandiono & Budiyanti 2023) reported that coffee intake raised systolic blood pressure
(SBP) and diastolic blood pressure (DBP) in 16 male and female teenagers. In another study, caffeine
withdrawal caused severe migraine attacks in majority of subjects (Alstadhaug etal., 2020).
10.6 REMOVAL AND MANAGEMENT OF PPCPS FROM WASTEWATER
Personal care items and pharmaceuticals have been identified as emerging polluters of water resources.
The wastewater containing PPCPs must be treated so that it does not impact the quality of aquatic
as well as terrestrial life. The standard environmental regulation allowed 50 ng/L of pharmaceutical
waste in discharged water (Rosman et al., 2018). The majority of pharmaceuticals are discharged
through urine and feces to sewage systems and effluents from industrial areas, hospitals and so
on. As a result, STPs/ WWTPs acquire varied amounts of different PPCPs (Bavumiragira & Yin,
2022). Different treatment methods have been explored for the removal of PPCPs which include both
conventional and advanced processes (Figure 10.3).
10.6.1 Different methods of management
10.6.1.1 Conventional systems
10 . 6.1 .1.1 Chl o r i n e
The most popular conventional method for sanitizing drinking water is still the treatment with
chlorine. Studies have shown that chlorine reacts rapidly with amine-containing pharmaceuticals
and gives rise to chlorine-containing products (Pinkston & Sedlak, 2004). For instance, chloramines
are produced when fluoxetine and metoprolol react with chlorine (Bedner & MacCrehan, 2006a).
Acetaminophen, the active ingredient in paracetamol, interacts with chlorine to produce a number
of byproducts, two among them (1, 4-benzoquinone and N-acetyl-p-benzoquinone imine) have been
recognized as hazardous chemicals (Bedner & MacCrehan, 2006b). But when chlorine is used
with UV it is reported to destroy PPCPs like 17a-ethinylestradiol, benzotriazole, carbamazepine,
chloramphenicol, diclofenac, iopamidole, metoprolol, and sulphamethoxazole (Pai & Wang, 2022).
10.6.1.1.2 Wastewater treatment plants (WWTPs)
WWTPs have a basic system of biophysical treatments and an additional system made up of an active
sludge-based biological reactor. As reviewed by Rivera-Utrilla etal . (2013), most of the PPCPs in urban
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192 Detection and Treatment of Emerging Contaminants in Wastewater
wastewater cannot be utilized by microorganisms and may even inhibit their activity or cause their
bioaccumulation in the food chain. The conventional WWTPs have a limited capacity to eliminate
pharmaceutical products from the wastewater. This study concluded that a significant portion of the
PPCPs contained in urban wastewater cannot be entirely removed by traditional treatment techniques,
as a result, they persist in effluents and pollute surface and underground waters, the primary sources
of drinking water. To lessen the environmental impact and potential harm caused by effluents, more
efficient and targeted treatments are needed.
10.6.1.2 Membrane filtration
It has been established that the majority of contaminants can only be partially eliminated by traditional
wastewater treatment methods. Therefore, to stop the release of PPCPs into the environment,
improvements in existing wastewater treatment methods and further treatment of the generated sludge
are needed (Kumar etal., 2023). Comparatively, more sophisticated wastewater treatment techniques,
like those utilizing membrane technology, can remove drugs at higher rates. Fundamentally, membrane-
based filtration techniques are classified into four basic types: microfiltration (MF), ultrafiltration (UF),
nanofiltration (NF) and reverse osmosis (RO). NF and RO membranes (due to their small pore size,
0.001–0.008 µg) have been suggested to be used effectively for the removal of pharmaceutical products
from wastewater (Yo on etal., 2006). But a smaller-sized compound can cross these filters and fouling
often occurs when cake is formed on a membrane’s sur face, which greatly decreases the overa ll separation
performance. On the other side, after membrane separation operations, the disposal of concentrates
becomes another challenge that has yet to be resolved (Rosman etal., 2018). In an experiment conducted
by Liu eta l . (2023) the removal efficiency of RO membranes was analyzed for PPCPs like carbamazepine,
ibuprofen and triclosan and was found to be 97.47%, 98.93% and 99.01%, respectively.
10.6.1.3 Membrane bioreactors (MBRs)
In comparison to the traditional activated sludge system, MBRs that combine the traditional biological
method with membrane filtering technology, exhibit a number of advantages, par ticularly high biomass
concentrations, effective solid–liquid separation and a small footprint. Long sludge retention times
(SRT) can improve the elimination of some organic compounds, but it is still difficult to effectively
Figure 10.3 Schematic diagram showing different methods for removal of PPCPs from wastewater.
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193Fate and behaviour of pharmaceutical and personal care products in wastewater
remove developing pollutants like PPCPs. Furthermore, due to the negative effects that antibiotics
have on microorganisms, a serious membrane fouling was seen in the MBR system while treating
antibiotics (Chen etal., 2020).
10.6.1.4 Activated carbon
Due to its adaptability and effectiveness, adsorption is a particularly intriguing method for the removal of
PPCPs. Since activated carbon (AC) does not produce toxins, it can be employed for adsorption (Delgado
etal ., 2019; Zhu etal., 2022). The most widely used ACs come in two forms, granular or powdered (GAC
or PAC, respectively). Both GAC and PAC can be used for the treatment of wastewater, however, PAC is
typically more effective with faster adsorption rates (owing to the smaller size of the particles) and GAC
has the primary benefit of regeneration/reuse post saturation (Delgado etal., 2019). Activated carbon
has been produced from Albizia lebbeck seed pods for the removal of cephalexin (Ahmed & Theydan,
2012), lotus stalk for removal of trimethoprim (Liu etal., 2012), and paper mill sludge for the removal of
citalopram (Calisto etal., 2 014). Even though ACs from different raw materials are widely available, a lot
of work is still being done on producing carbons from different starting materials (like agricultural and
industrial residues) to reduce production costs and encourage value-added recycling of waste (Calisto
etal., 2 014). The primary objective is to produce a carbon with a high adsorption capacity using low-
cost, ecologically acceptable methods (without utilizing external activation method) and, at the same
time, to suggest a novel approach to valorizing the industrial byproducts (Calisto etal., 2014).
10.6.1.5 Advanced oxidation processes (AOPs)
These pr ocesses mai nly use higher concentrations of hydroxyl radicals which transform the recalcit rant
PPCPs by reacting with them through chemical or photochemical reactions like photooxidation,
ozonation and electrochemical oxidation (Rosman etal., 2018).
10.6.1.5.1 Photooxidation
When photon energy from artificial or natural light interacts with the target molecule, it triggers
a photochemical reaction that causes the target contaminant to mineralize, this process is called
photolysis (Rosman etal., 2018). The radiation wavelength within ultraviolet spectrum that is 200–
400 nm is commonly used for photolysis. A number of pharmaceuticals can undergo degradation upon
absorption of solar radiation while some others like ibuprofen, naproxen, triclosan and triclocaban
are not photoactive or produce toxins upon photooxidation (Rivera-Utrilla etal., 2013).
10.6.1.5.2 Ozonation
For ozonation, a number of reagents can be used to increase the oxidation reaction in the form of
O3/H2O2, O3/U V, O3/H2O2/UV and O3/activated carbon systems for the removal of pharmaceuticals
from water. In recent years, this method has attracted a lot of interest among researchers worldwide
(Rivera-Utrilla et al., 2013; Rosman et al., 2018). Ozone (O3) instability encourages a spontaneous
breakdown with a water matrix component to produce a hydroxyl group (⋅OH). This process of ozone
breakdown occurs at a basic medium (i.e., at high pH) (Rosman et al., 2018). According to Adams
et al. (2002), ozonation effectively removes paracetamol from wastewater. Further, the addition of
H2O2 accelerates the process of ozone breakdown as the reaction of O3 and H2O2 results in a radical
chain mechanism that produces hydroxyl radicals (Rosman et al., 2018). For instance, clofibric acid
and ibuprofen cannot be effectively eliminated by ozone alone but can be successfully removed by O3/
H2O2 (Snyder etal., 2006). UV rays may be used during the ozonation process in place of peroxide as
the oxidizing agent. UV works by giving the energy to chemical compounds through radiation that can
be absorbed by reactant molecules, which can then move into an excited state but require a lot of time
to complete the reaction (Balcioglu & Otker, 2004). For the treatment of water, several researchers
have investigated O3/UV or O3/H2O2/UV combinations. The most potent oxidation process when
compared among O3/H2O2, O3/H2O2/UV and O3/UV is O3/H2O2/UV (Rosman etal., 2018).
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194 Detection and Treatment of Emerging Contaminants in Wastewater
10.6.1.5.3 Electrochemical oxidation
Due to their compatibility with environmental conditions, simplicity and ease of automation,
electrochemical oxidation process is the most widely used electrochemical method for wastewater
cleanup. The electron transfer occurs between the electrode (anode) and the pollutant. The material
of the electrode has a significant impact on the electrochemical process because some anodes prefer
partial oxidation while others prefer the selective oxidation of organic pollutants. Comninellis (1994)
classified the anodes into two types, the active anodes (Pt, IrO2 and RuO2) and the non-active anodes
(PbO2, SnO2 and boron-doped diamond (BDD)). Water is oxidized in both types of anodes, designated
as M, producing a physiosorbed hydroxyl radical (M(OH)). This radical interacts so intensely with the
surface of ‘active’ anodes that it is converted to chemisorbed ‘active oxygen,’ or superoxide MO. As
opposed to this, the surface of ‘non-active’ anodes only weakly interacts with M(OH), and this radical
then directly reacts with organics until entire mineralization is reached. The BDD anode is considered
as the most effective ‘non-active’ electrode available and is regarded as the best anode for treating
PPCPs via advanced oxidation (Marselli etal., 2003).
10.6.1.5.4 Fenton oxidation
The Fenton reaction produces extremely reactive hydroxyl radicals by decomposing hydrogen peroxide
with ferrous ions (the reaction occurs at an optimum pH range of 2.8–3.0) (John etal., 2022). Fenton
technolog y, among several AOPs , has the benefit of com paratively m inimal re actions, an e asy techn ique,
and a high oxidation capacity, making it an intriguing option for the management of PPCPs. However,
typical Fenton technology has various limitations, including significant iron loss, a limited pH range,
and the difficulty of Fe2+ recovery in practice (Qian et al., 2021). To address these disadvantages,
considerable work was invested in the conceptualization and creation of heterogeneous Fenton-like
catalysts. There are methods like electro-Fenton oxidation (generation of H2O2 by electrolysis), bio-
electro Fenton process (electricity for H2O2 generation is produced by electrochemically active cells
i.e., microbial fuel cells) (Wang etal., 2018), photo-Fenton process (Fenton oxidation in presence of
artificial light sources) (Guo etal., 2023) and so on. The research is still going on and new reaction
mechanisms are being discovered, so, it is difficult to classify a single AOP as the best method for
removing PPCPs from contaminated water.
10.6.1.6 Constructed wetlands
Constructed wetlands are artificial ecosystems constructed in a specific environment, primarily
used for wastewater treatment. Macrophytes, substrate for macrophyte growth, water depth, wetland
structure and proper hydraulic retention time (HRT) are just a few of the many criteria that must be
carefully measured for CWs to operate well. CWs are regarded as more effective and sustainable for
treating various PPCPs. The use of CW systems can remove more than half of all PPCPs under ideal
circumstances. The macrophytes remove PPCPs by elimination (under favourable conditions) or by
direct uptake (Kumar et al., 2022). Li et al. (2014) reported the degradation of ibuprofen, caffeine
and naproxen by using CWs. The biomass produced by macrophytes can be used as raw material in
industries (paper and pulp), for biofuel production and so on. Although CWs have advantages over
other methods of PPCPs removal, there are studies that showed that the presence of excess organic
matter, the number and type of PPCPs, pH and temperature reduce the degradation/absorption
efficiency of CWs (Kumar etal., 2022).
10.7 CONCLUSION AND FUTURE PROSPECTIVES
In conclusion, the presence and persistence of PPCPs in wastewater have raised serious concerns about
potential environmental risks. Humans use these chemicals heavily on a daily basis, and they can
enter the ecosystem in a number of ways, including veterinary and human medications, nutraceuticals,
bioactive food supplements, wastewater treatment facilities, PPCP manufacturing industries, agricultural
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195Fate and behaviour of pharmaceutical and personal care products in wastewater
runoff and natural cycles. When PPCPs are added to sewage or wastewater, they go through a variety
of transformations. Because traditional sewage treatment (STPs) and wastewater treatment plants
(WWTPs) were unable to properly process these chemicals, various advanced methods such as
membrane filtration, MBRs, activated carbon and advanced oxidation processes (which appear to be
promising) have been suggested. Due to their bioaccumulation and biomagnification, these substances
may have a number of negative impacts on the aquatic ecosystem and disrupt the food chain which
ultimately puts human health at risk. This necessitates the development of better wastewater treatment
technology that specifically targets PPCPs. Exciting opportunities for sustainable management exist as
a result of the future predictions for the fate and behaviour of PPCPs in wastewater. Enhancements in
treatment technologies, encouraged by ongoing research and development initiatives, will increase the
effectiveness of PPCP removal. The amount of PPCP released into wastewater will be reduced by the
incorporation of source control measures, regulations and public awareness campaigns. Potential harm
will be reduced through environmental risk evaluations and the establishment of safe concentration
limits. The sustainability of resources will be greatly impacted by resource recovery and water reuse. We
can ultimately create a path towards efficient PPCP management in wastewater, protecting both human
and environmental health, through cooperation among researchers, policymakers and stakeholders.
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© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0203
Masixole Sihlahla1,2,4 and Sihle Mngadi1,2,3*
1Department of Chemical Sciences, University of Johannesburg, Doornfontein Campus, P.O. Box 17011, Johannesburg 2028,
SouthAfrica
2Department of Science and Innovation-National Research Foundation South African Research Chair Initiative (DSI-NRF SA RChI) in
Nanotechnology for Water, University of Johannesburg, Doornfontein 2028, South Africa
3Scientific Services, Laboratories, Chemical Sciences, uMngeni-uThukela Water, Pietermaritzburg, South Africa
4Department of Chemistry, College of Science and Engineering and Technology, University of South Africa, Johannesburg,
SouthAfrica
*Corresponding author: sihlemngadi1966@gmail.com
ABSTRACT
This chapter focuses on reviewing the literature that provides reliable and quantitative information on emerging
contaminants (ECs) in wastewater, focusing on their occurrence, detection and removal efficiency using advanced
analyt ical techniques . In addition, providi ng knowledge on area s of ECs that are non- regulated since t he environmenta l
legislations and policies are being developed. Some of the classes of ECs include pharmaceuticals, nanomaterials,
herbicides, personal care products and microplastics and many more. ECs have been identified as an environmental
problem globally and are a result of different compounds ranging from inorganic to organic compounds which are
released into the environment. ECs are commonly found in aquatic environments and the main source of ECs are
municipal wastewater, domestic discharge, hospital effluents, industrial wastewater and agricultural run-off. The
presence of ECs poses health problems and ecological impacts associated with them. The elevated concentration
of ECs in wastewater has necessitated a need to research their varying detection techniques and different ways
of removal. Water contamination by ECs is also attributed to an increase in urbanization, industrialization and
agricultural activities. Current wastewater treatment plants are inefficient in the removal of ECs as they were not
initially designed for the treatment and removal of ECs, these may result in the transformation of EC products that
are undetected and unregulated. These products exhibit similar toxicity as their parental ECs, while some of the
ECs have been recognized as endocrine-disrupting chemicals. Due to new ECs being introduced, there is a gap in
knowledge of their detection and treatment techniques for their removal, thus demonstrating a need for integrated
analytical approaches that compliments the screening and removal of target and non-targeted ECs with biological
assays. Development advancement of analytical techniques has enabled the detection, identification and treatment
of ECs in trace concentration (mg to ng/L), and the development and advancement of hybrid treatment systems
are emerging promising treatment solutions. The use of nanomaterials and phytoremediation approaches are new
approaches widely studied as a good potential process for remediating the ECs in wastewater.
Keywords: emerging contaminants, wastewater, advanced analytical techniques, occurrence, detection and
removal
Chapter 11
A review of occurrence of emerging
contaminants and the advanced
analytical techniques used for
detection and removal of these
pollutants in wastewater
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204 Detection and Treatment of Emerging Contaminants in Wastewater
11.1 INTRODUCTION
Emerging contaminants (ECs) consist of extensive and broader groups of human-induced/
anthropogenic compounds frequently present within wastewater but currently have been recognized
as major pollutants for terrestrial and aquatic environments (Ifon etal., 2023; Pal etal., 2023). ECs
are defined as a wide range group of synthetic or naturally occurring chemical compounds, these
compounds have adverse effects on humans, animals and the environment (Kadac-Czapska e t al.,
2023). ECs include a diverse amount of substantially utilized compounds and products such as
artificial sweeteners, pharmaceutical and veterinary drugs, pesticides and herbicides among others
(Figure 11.1). ECs are commonly distributed throughout the environment but are predominantly
present in wastewater effluents (Hu etal., 2023; Kadac-Czapska etal., 2023).
The monitoring and control of ECs increase within the environmental compartments has proven
to be a very strenuous task because these compounds are present in our essential products such as
pharmaceuticals and personal care products (PCPs) that we use daily. Apart from the increasing
use of ECs in daily essential life activities and a surge in environmental pollution through these
contaminants, the disadvantageous health effects caused by bioaccumulation and biomagnification of
ECs within the environment cannot be disregarded (Jaffari etal., 2023). However, the occurrence of
ECs in effluent discharge from wastewater treatment plants (WWTPs) is fundamentally impacted by
population density, geolocations and usage patterns of ECs containing products and materials (Parida
etal., 2021). The industrial and urbanization developments have led to an increase in new chemicals
containing ECs being produced and used in daily activities which represents a concern for authorities,
researchers, the general population and the environment (Ren et al., 2023a, 2023b). The inherent
hazard they pose to human health has attracted public interest and the adverse environmental impact
is due to their continuous discharge and environmental pollution without proper monitoring protocols
being implemented (Bellas & León 2023; Majumder etal. 2023; Ullah etal., 2023).
Figure 11.1 Different classes of emerging contaminants.
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205A review of occurrence of emerging contaminants
The technological advancement of analytical methodologies and instrumentation have empowered
researchers in identifying, detecting and quantification of a wide range of ECs that are found in
low concentrations within aquatic environments such as wastewater, drinking water, surface and
groundwater analysis studies (Hanna et a l ., 2023; Hawash e t a l ., 2023; Milanović et a l . , 2023). Research
work conducted on wastewater and WWTPs has gained attention in environmental assessments due
to a variety of recently identified and quantified compounds/pollutants that are present because of
anthropogenic activities (Martínez-Huitle e ta l . , 2023). Many studies recently documented in literature
have reported on the occurrence of EC pollutants within the environment, which are present in a
wide range of concentrations from micrograms per litre (µg/L) to nanograms per litre (ng/L). These
pollutants are commonly classified as ECs and do not have any legislative regulations or guidelines.
These pollutants are a concern to environmentalists and healthcare workers as they pose adverse
health effects and are undetectable in conventional WWTPs and effluent discharge and are not
regulated (Ofrydopoulou etal., 2022).
The detection of various new ECs compounds in various water bodies has highlighted the health
and safety concerns as these pollutants are potentially hazardous to human and animal consumption
and have been deemed to be unsafe (Barbosa et al., 2023). The occurrence of ECs within the
environment results in human and animal health implications and environmental endangerment
(Ghasemi etal., 2023; Kumar etal., 2022). The presence of ECs has been identified in various water
bodies such as surface and groundwater, as well as wastewater that is discharged from treatment
plants (Puri et al., 2023). The existence of these pollutants within the environment may pose
various health risks to humans and animals such as cancers, endocrine disruptions, neurotoxicity,
reproduction problems, bacterial resistance and feminization in aquatic species among other health
problems (Shanmuganathan etal., 2023). The detection and removal of ECs in the environment has
become an extreme environmental concern and has proven to be greatly imperative in expanding
the efficiency of wastewater treatment methodologies in combating and removal of EC pollutants.
Although concentration levels of EC compounds are vastly different globally when in comparison
between continents, countries and also at a regional scale (Martínez-Huitle etal., 2023). A major
source of EC contamination has been identified as untreated wastewater and effluents discharged
from WWTPs. The majority of current WWTPs were not intentionally designed to remove ECs
and transformative by-products that are subsequently discharged into various aquatic bodies. In
addition, the current knowledge available is inadequate to enable the development of new innovative
analytical methodologies that can be used to monitor and control the release of ECs from WWTPs
into the environment (Krishnan et al., 2023). It has been reported that the majority of ECs are
non-biodegradable and persistent and to overcome this disadvantage, newly developed advanced
WWTPs have to be equipped with treatment methods to improve the effluent concentration of
EC and wastewater management which will help to comply with new strict/ rigorous discharge
regulations and laws applied. Therefore, to preserve and safeguard water bodies from such pollutants,
the following alternatives must be scrutinized:
• Identifying the source of ECs and inspecting the wastewater quality
• Evaluation and identific ation of hazardou s effects of ECs on t he environme nt, humans and anim al
health, and these would be possible by assessing the nature and toxicity of these compounds and
their transformative by-products produced during various stages of water treatment procedures
• Develop or improve WWTPs technologies for wastewater treatment processes that will reduce
the discharge of ECs and environmental impacts caused by ECs
• Conduct environmental assessments to monitor the discharge.
Other sources of ECs include the fertilizer industry, adhesives, food and drinks packaging and fire
retardants among others (Dubey etal., 2023; Faisal etal., 2023; Sathya etal., 2023). Conventional
WWTPs removal of ECs via common processes is regularly time-consuming. These common
processes are facilitated by various characteristics such as the type of target ECs and the accessibility
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206 Detection and Treatment of Emerging Contaminants in Wastewater
of microorganisms that can degrade the ECs present. Consequently, there is a heightened requirement
to investigate and apply efficient methods for the removal of ECs in wastewater (Ali etal., 2023).
ECs enter the food chain in diverse routes and result in the biomagnification of these compounds.
Consequently, an increment of ECs concentrations in living organisms at sequential trophic levels
can be observed in the food chain animals (Almazrouei et a l., 2023). Extended exposures to ECs
induce adverse effects on the aquatic ecosystems, and at times modify the hormonal and metabolic
mechanisms of humans and animals (Gunathilaka e t al., 2023). The toxicity of EC compounds is
driven by various factors; namely their chemical structure, the body’s ability to absorb ECs and
detoxification ability of the body. The chemical, physical and ecotoxicity profile of EC compounds are
associated with its distinctive molecular structure, and the toxicity is assessed based on the functional
groups attached to the compound, their reactivity and by-products (Korzeniowski etal., 2023; Parida
etal ., 2021). The primary pathway for human exposure to ECs is via the consumption of foods, animal
products and drinks that are associated with contaminated water, soil, plants, microorganisms and
animals (Chaturvedi et a l., 2023; Interdonato et al., 2023) (Figure 11.2). This can be exhibited as
bioaccumulation of ECs, especially for the species placed on top of the food chain (du Plessis etal.,
2023; Thacharodi etal., 2023).
Immediately when ECs or their transformative by-products reach environmental partition, they can
experience different mechanisms such as absorption, adsorption, hydrolysis, dilution, biodegradation,
complexation and chemical oxidation among other processes. Each of these processes possesses the
ability to result in the degradation, transformation or persistence of ECs within the environment
(Lofrano etal., 2020).
Various review studies have focused on the occurrence of ECs in different environmental matrices
especially in freshwater bodies and wastewater (Foglia etal., 2023). Some of the review studies have
also analysed the present instrumentation and methodologies used for the detection of ECs and their
Figure 11.2 Adverse effects of emerging contaminants on animal and human health as well as on the environment.
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207A review of occurrence of emerging contaminants
removal and remediation procedures. A handful of the current review studies have attentively focused
on the available current removal and treatment techniques such as advanced oxidation process
(AOPs), coagulation, adsorption, membrane-based and flocculation among others for removal of ECs
in wastewater. Other studies have focused on the application of biological techniques for removal
of ECs such as microalgal removal of ECs in wastewater (Ramesh et al., 2023). Some studies have
focused on bioremediation and biotransformation of ECs and converting them into less/ non-toxic
by-products in wastewater, while other studies have highlighted the environmental impact, risks,
ecotoxicity and health concerns of ECs and their removal (Puri et al., 2023). Present-day studies
have investigated the application of biochar and activated carbon (AC) among others as adsorbent
materials to remove ECs from wastewater (Alyasiri etal., 2023).
Nevertheless, discussing and understanding the recent progress researchers have made on ECs,
feasibility, advantages and limitations in the development and application of novel techniques for
the detection and removal of ECs are important to implement and integrate using a robust low-cost
approach within conventional WWTPs. Therefore, according to the best knowledge of the authors,
a broad study on occurrence, detection, removal techniques from wastewater and a summary of
ECs health and environmental impacts have not been efficiently structured in one study present in
literature studies.
Therefore, this current book chapter critically examines the recent literature research work and
innovative developments and advancements in the detection and removal of ECs from wastewater,
with in-depth research on the types of ECs, health concerns, sources and environmental occurrence.
In addition, the economic feasibility of implementation of these removal techniques, the advantages
and disadvantages associated with different removal techniques have been discussed. The review
chapter also imparts awareness of the future perspectives for research work and legislative policies
and strategies that can be implemented to monitor and minimize the release of ECs.
11.1.1 Review methodology
The most relevant literature review was obtained from established trustworthy databases such as
Google Scholar, Scopus, Science Direct and among other reliable information sources. The following
terms were used as keywords during the search process: Emerging contaminants (ECs); toxicity of
emerging contaminants; Occurrence of ECs; detection of ECs; physiochemical, biological, chemical
and removal and remediation process of ECs; emerging hybrid removal and remediation process of
ECs. The current review chapter aims to analytically provide critical information on existing literature
on emerging contaminates, newly developed remediation techniques of ECs from wastewater and
high lights t he knowledge on removal t echniques and i mplementation of hybr id technologies for r emoval
of ECs and wastewater remediation. This review chapter also outlines the existing data in highlighting
key areas for future research which would assist in addressing gaps in existing knowledge/literature.
Especially regarding upscaling and implementation of new ECs removal techniques and application of
hybrid techniques. In addition, this review chapter highlights the commercial feasibility of the current
techniques and recommends a handful of propitious innovative policy-based perspectives. This chapter
investigates the challenges associated with ECs ranging from occurrence, health and environmental
impacts, and innovative treatment techniques. The interest in research studies based on ECs has
evidently escalated over the past decade, therefore, this work provides state-of-the-art information on
ECs with a specific focus on recent developments and advancements in the occurrence, detection and
removal techniques of ECs.
11.2 OCCURRENCE
Various factors influence the occurrence of ECs in the environment, the major factors being the physio-
chemical properties of the environment and the wastewater. In addition, the type of source for the ECs
influences the exposure degree and the properties of ECs (Majumder etal., 2023). Most studies present
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208 Detection and Treatment of Emerging Contaminants in Wastewater
in the literature have identified municipal wastewater discharge as a major source of ECs. Other
sources (non-point and point) such as stormwater, household and hospital, industrial wastewater, and
agricultural run-off have also been identified as sources of ECs (Coxon & Eaton, 2023).
Current research has pivoted more on the occurrence and detection of ECs in influents and effluents
(Dubey et al., 2023). On the other hand, the particulate phase, which includes the sludge matrix,
has not been investigated in detail due to a lack of instrumentation techniques that can be used to
analyse such a sample matrix. However, the detection of these contaminants in the particulate phase
is important to assess the destiny and hazardous adverse influence on the environment and human
and animal health (Dubey etal., 2023).
Most of the ECs are discharged into the environment via different mechanism routes such as urine
and faecal matter in the case of drugs consumed by humans and animals, agricultural application
of wastewater, sewage sludge and manure, landfill leachate, manufacturing, industrial wastewater,
domestic use and release of products containing ECs. The major contribution of ECs to the environment
stems from anthropogenic activities such as conventional WWTPs effluent release, whereby ECs
are collected and accumulated from industry and urban discharge and are incompletely removed
(Sewwandi et al., 2023). Most conventional WWTPs comprise physical, chemical and biological
treatment systems which are not suitable in design aspects to efficiently remove ECs due to their
complex molecular structure, low concentration and non-biodegradable in wastewater (Figure 11.3).
The effluents generated from such W WTPs have been the most significant point source of ECs. Despite
advanced technologies implanted in urban W WTPs being able to remove ECs, their removal efficiencies
are limited well developed areas. For underdeveloped places with economic and technical limitations,
the use of advanced WWTPs is hindered. ECs will not easily be removed or bio-transformed into less
toxic compounds in wastewater, which leads to inefficient removal by current WWTPs systems. This
indicates that ECs can be effortlessly released from WWTPs and be discharged into the environment
Figure 11.3 Different pathways for occurrence of ECs.
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209A review of occurrence of emerging contaminants
compartments via direct disposal of wastewater. In addition, studies have been documented in the
literature that report low removal efficiency of ECs in conventional WWTPs that still use conventional
methods such as treatment of sludge, flocculation and sedimentation (Puri etal., 2023).
Various EC compounds go through microbially mediated reactions during the wastewater treatment
process. Biodegradation is often identified as the dominant pathway for the remediation of ECs from
wastewater, however, the use of biodegradation methods generally results in the transformation of
ECs into new compounds that are likely to be me hazardous and get discharged from WWTPs without
any detection or removal action (Douna & Yousefi 2023; Zambrano etal., 2023).
Sources of ECs within the environmental matrices are present in two forms namely the point
source and diffuse source (Onnis et al., 2023). Point source refers to contaminant pollution that
emanates from distinct locations whose pollution inputs into the environment can certainly identified
in a spatial distinct manner. Important examples of point sources include domestic, hospital and
industrial effluents, WWTPs effluents, sewage storm-water overflow, waste disposal sites, resource
extraction and buried septic tanks among others (Ulucan-Altuntas etal., 2023). Diffuse source refers
to contamination pollution that originates from poorly distinct locations that usually occur over a
wide broad geographical scale. Examples of such source points include stormwater and urban run-
off, leakage from sewage systems and diffuse aerial deposition, and agriculture run-offs from the
application of chemicals such as bio-solids, pesticides and manure among others (Niu etal., 2022;
Onnis etal., 2023).
Insufficient information on toxicity, impact and concentration levels of ECs present within various
environmental compartments results in problems for government and environmental authorities
to manage their application and also control their discharge levels. There are no laws in practice
regulating the upper permitted concentration levels of ECs in wastewater discharge, ECs present in
potable water or in the environment (Reid et al., 2019).
11.3 DETECTION
In the past couple of decades, tremendous progress has been made in the detection of ECs in
water treatment and industrial effluents and the development of new analytical methods for the
characterization, identification and quantification of rapidly evolving ECs (Hemida etal., 2023; Ieda
& Hashimoto 2023; van den Hurk etal., 2023). Various types of ECs are continuously discharged
into water surroundings either purposely or unintentionally, with little or no legislation in place or
minimal care thus posing a health risk to humans and animals (van den Hurk etal., 2023).
With the requirement to investigate the occurrence, transportation, and fate of ECs, it is important
to unequivocally identify the new ECs and determine their concentrations (Angelakis et al., 2023).
Majority of the EC compounds are easily soluble in water due to their chemical structure, therefore
posing a potential harm to the human, animal and aquatic life through the water cycle. There has been
an increase in the number of ECs detected in the environment (drinking, ground, surface and waste)
comprising of parents and their derivatives. The identification and assessment of ECs in water have
proven to be an important task scientifically, which requires highly sensitive analytical techniques
capable of reaching the nanogram per litre (ng/L) scale. The analysis of ECs must be conducted using
sensitive, selective, robust and automated techniques that apply to a wide range of compounds that
are present in wastewater. Therefore, there is a need for the development of methods that are fast,
responsive and efficient in the detection and determination of the wide range of ECs which in turn
can be used for monitoring purposes (Ghosh et al., 2023; Kumar etal., 2022). There are different
analytical methods have been investigated by researchers globally for the analysis of ECs in wastewater
(Kumar etal ., 2023). In W WTPs, different water samples such as influent and effluent are the common
matrices that are mostly used in the development stages of analytical techniques that can be used
for the efficient qualitative and quantitative target analysis of ECs (Ghosha & Biswasb, 2023). Mass
spectrometry coupled liquid chromatography (LC–MS) or tandem MS has been recently upgraded for
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210 Detection and Treatment of Emerging Contaminants in Wastewater
analysing ECs in different matrices like solid sludge and water at low extreme concentrations (ng/L or
µg/L). In the field of environmental analytical chemistry, these advanced techniques have been widely
used for the detection and quantification of over 3000 active chemicals (Angelakis etal., 2023).
The an alysis of ECs e ssential ly needs a method w ith a low limit of det ection (LOD) and hi gh selectiv ity.
Analytical instrumental analysis of ECs in wastewater is generally conducted by chromatographic and
spectrochemical techniques which are coupled to mass spectrometry (MS) (Li et al., 2023). ECs are
mostly polar compounds, and their analysis by gas chromatography (GC) is hindered by limitations
of volatility and/or thermal stability. These above-mentioned limitations can be overcome by the
application of derivatization processes such as silylation, acylation and alkylation among others. The
application of the GC for the detection of ECs has proven to be an inexpensive technique that could be
implemented in different laboratories globally. Most GC methods reported in the literature are coupled
to MS detection in both tandem and single modality (Angelakis etal., 2023). GC commonly demands
the addition of a derivatization step which would help improve the chromatographic behaviour of
analytes while also improving selectivity, sensitivity and peak resolution (Li etal., 2023).
Despite the advantages provided by GC, the liquid chromatography (LC) based methods are the
most commonly used for ECs detection in wastewater (Khurana etal., 2022). LC provides a higher
versatility in the analysis as it covers a wide range of compounds that can be detected without the
need for derivatization. The choice of detection preferred with most LC methods is the MS. Within LC
techniques, high-performance liquid chromatography (HPLC) has emerged as an improved modality
along with ultra-high version (UHPLC) (Chaturvedi etal., 2023). Most of the ECs are usually found
at ppb to ppt levels in different environment matrices, therefore, liquid chromatography with tandem
mass spectroscopy (LC-MS/MS) is used. The major advantage of the LC-MS/MS is the high selectivity
and sensitivity (Khurana et al., 2022). Volatile organic compounds are usually analysed using GC,
while LC is utilized for detecting polar and less volatile compounds. The MS techniques have shown
outstanding results in precise analysis of ECs that are present within complex matrix samples of
wastewater (Sewwandi etal., 2023). GC–MS and LC–MS have been extensively used for analytical
analysis of ECs including pharmaceuticals and metabolites, endocrine disrupting compounds, UV
filters and flame retardants among others.
Inductively coupled plasma mass spectrometry (ICP-MS) has been used for the analysis of
nanomaterials detection in wastewater. This technique provides some advantages such as low LOD,
high precision, low cost and simultaneous analysis of multi-elements and isotopes within a few minutes
(less analysis time required). The coupling of ICP with various detectors has also been used for the
analysis of nanomaterials. Improved detection limits of the ECs to low concentration are achieved by
these analytical instruments (Gumbi etal., 2022; Inarmal et al., 2023).
Recently, most studies focusing on the detection of the ECs have been successful through using
sophisticated instrumentation which includes, gas chromatography/mass spectrometry (GC/MS),
GC/MS/MS, ultra-high-performance liquid chromatography–tandem mass spectrometry (UHPLC/
MS/MS), triple quadrupole mass spectrometer (TQ-MS), high-performance liquid chromatography
(HPLC) and LC–electrospray tandem MS (LC–ES/MS/MS) (Table 11.1). The application of these
techniques ensures low concentration up to ppt levels with good precision and accuracy.
Currently, there is insufficient data in global comparison studies on the detection, analysis and
occurrence of ECs in wastewater and other water bodies. A study conducted by Nikolopoulou etal.
(2023), on the investigation of ECs examines water samples obtained from three separate WWTPs
in Lagos, Nigeria. The detection and identification approach were executed using ultra performance
liquid chromatography mass spectrometry (UPLC-QToF-MS), 250 compounds were identified in the
samples analysed from the WW TPs. A total of 182 compounds were quantified from the 250 detected,
and 78 of those compounds had a high significant environmental risk score index. The majority of the
compounds detected at high concentrations were pharmaceuticals and were from hospital WWTP,
with salicylic acid having the highest concentration of 72.4 mg/kg followed by ciprofloxacin and
ofloxacin at 24.4 and 28.4 mg/kg, respectively.
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211A review of occurrence of emerging contaminants
Ng etal. (2023), conducted a study using state-of-the-art target screening approach for 2362 ECs
compounds and their transformation by-products. The analysed ECs included three major categories:
industrial chemicals, plant protection products (PPPs) and (PPCPs). A total of 586 in the samples
which consisted of 158 PPP’s, 71 industrial chemicals, 348 PPCPs and 9 other chemicals. The sample
variety used in the study consisted of influent and affluent wastewater, groundwater and river water.
Gas chromatography–high resolution mass spectrometry (GC–HRSM) and LC–MS/MS were used for
the detection and analysis of ECs compounds respectively.
11.4 REMOVAL
11.4.1 Physiochemical methods
Physicochemical mechanism is one of the widely used approaches used to remove the ECs from
wastewater and surface waters through sorption onto biomass during wastewater treatment (Tholozan
et al., 2023). The removal of pathogens, odour and reduction of turbidity is generally assisted by
the physio-chemical treatment process. These processes provide the advantage of decreasing the
pollutants in drinking water, however, their removal efficiencies have been proven insufficient for
ECs. Coagulation–flocculation is the standard physio-chemical process that is usually necessary for
Table 11.1 Different detection techniques of ECs.
Source Country Detection
Technique
EC Analysed Concentration References
River China LC/MS/MS Antibiotics 0.1 and 74 ng L−1Chung etal.
(2016)
River USA LC–MS/MS Sulfamethazine,
tylosin, and atrazine
1.87, 0.30, and
754.2 ng/L
Albero etal.
(2018)
Surface water South A frica and
Botswana
LC–MS Antiretroviral drug
ritonavir; ibuprofen 64.52 µg/L; 1097 Selwe etal.
(2022)
Waste and
surface
South Africa Triple TOF
coupled
LCHPLC
Pharmaceuticals,
drugs, and
metabolites.,
personal care
products, pesticides
and food additives
ng.L−1 to µg.L−1Abafe etal.
(2023)
Freshwater,
marine and
terrestrial
apex predators
United Kingdom,
Ger many,
Netherlands and
Sweden
LC–HRM Pharmaceuticals
and antibiotics ng.L−1 to µg.L−1Gkotsis etal.
(2022)
Rivers and
wastewater
China (UPLC–MS/
MS)
Antidepressants 0.6 and 87 ng/L Karlsson
etal. (n.d.)
Surface water India LC/Q–
TOF-MS
Pharmaceuticals
and agrochemicals ng.L−1 to µg.L−1Richards
etal. (2023)
Surface water Brazil LC–MS/MS
with (ESI)
and HPLC
Pharmaceutical
products and
herbicides
4.6 to 14.5 µg L−1Gomes etal.
(2022)
Wastewater South Africa SPE and
(LC–MS)
Sulfamethoxazole
hydroxylamine,
sulfamethoxazole,
prednisolone and
ivermectin
0.05215
0.979 mg/L
Inarmal and
Moodley
(2023)
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212 Detection and Treatment of Emerging Contaminants in Wastewater
water treatment processes. The removal of ECs using physiochemical methods is divided into two,
that is membrane and adsorption techniques (Jaffari etal., 2023).
11.4.1.1 Adsorption methods
The adsorption treatment process is common and important in water treatment due to its simplicity
in design and it yields by-products and has proven to be insensitive to toxic substances. Adsorption is
defined as a phenomenon of accumulation of analyte(s) material onto the adsorbent material. The use
of adsorption techniques for the removal of EC’ from wastewater has been explored and recorded in
the literature (Kordbacheh & Heidari, 2023).
The adsorbent materials adsorb the target analyte(s) on their surface comprised of porous networks
and consequently eliminate the pollutants from the wastewater. Adsorbent materials generally have
features of large surface area and high porosity. The adsorption process has been established to be
an excellent method aimed at the separation and elimination of dilute contaminants and provides
benefits such as recovery, recycling and reuse of the adsorbent material (Rathi & Kumar, 2021).
A widely used adsorbent material is activated carbon which could be differentiated into two
groups namely powdered activated carbon and granular activated carbon (Figure 11.4). The main
disadvantage of commercial activated carbon is the high production and regeneration costs. Even
after activated carbon adsorbent has been used, it can also be regenerated for future use. However,
the regeneration process can result in carbon loss thus resulting in the production of adsorbent
with lower adsorption efficiency when compared to freshly prepared activated carbon. Currently,
there’s a developing interest in alternative low-cost adsorbent materials derived from waste materials
or by-products from agricultural or industry processes. The removal efficiency of these adsorbent
materials is based on their properties such as porosity, surface area, pore diameter, functional groups
and the chemical nature of the specific target ECs. In addition, the existence of dissolved organic
matter may affect the efficiency of the adsorption process. The occurrence of dissolved organic matter
within might result in competition for the available adsorption site with the target analyte(s) and thus
resulting in reduced adsorption capacity for ECs (Kurniawan etal., 2023).
Figure 11.4 Treatment techniques commonly used for removal of emerging contaminants in wastewater.
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213A review of occurrence of emerging contaminants
Filtration processes using membrane methods such as reverse osmosis, micro, nano and
ultrafiltration depending on the pore size and separation mechanisms are generally used in WWTPs to
remove ECs. The advantage of the membrane filtration technique is the high value of eluent discharged
without the need for the addition of other purification chemicals. Membrane filtration methods are
now commonly applied to WWTPs for wastewater treatment reclamation and drinking water as they
have been proven to efficiently remove the majority of organic and inorganic pollutant compounds
(Nikolopoulou et a l., 2023). The implementation of reverse osmosis and nanofiltration techniques
have been proven as capable alternatives for removing ECs in wastewater processes, occurring in
three steps as follows:
Step 1: The adsorbate material (analyte (s) is transferred to the exterior surface of the adsorbent
material, and this process is driven by film diffusion which is also known as the external
diffusion mechanism.
Step 2: This is a movement of the analyte(s) from the adsorbent surface into the adsorbent pores
which is also known as the porous diffusion mechanism.
Step 3: The analyte(s) material is fixed/retained on the adsorbent pores and this is known as the
adsorbate surface reaction mechanism.
The adsorption treatment process is identified as user friendly and reliable wastewater treatment
process owing to the versatility of usage as it provides its lack of sensitivity to unsafe materials, and
its ease of operation (Raninga etal., 2023).
Several adsorbents are utilized in wastewater treatment plants to remove emerging contaminants,
and these include carbon materials, polymers, activated carbon, activated carbon, metal–organic
complexes, carbon nanotubes, zeolites, organic carbon complexes, mineral substances, carbon
nanotubes, biochar and amongst others. These adsorbents may originate from several materials,
and these include plants, carbon nanotubes, fly ash, ion exchange resin, some minerals, organic
resins and so on. Some of the requirements of these adsorbents are that they must be efficient,
effective, cost-effective, greener to the environment and have good regeneration capacity (Sellaoui
etal., 2023)
Based on the literature that was recently published, the adsorption process is regarded as the
greener approach for the removal of ECs from wastewater resources. This is because the process is
capable of removing a high percentage of ECs with lesser secondary sludge generation. Furthermore,
this process can be combined with other systems, and thus increases the removal efficiency (Coxon
& Eaton, 2023).
11.4.1.2 Membrane technology
This treatment technology involves the filtration of the solution by retaining the analyte(s) on a
membrane material and the target analyte(s) that are removed are analysed by different filtration
characteristics such as surface charge, pore size and hydrophobicity which are based on the
membrane properties (Ghasemi etal., 2023). To combat the growing concern about ECs, high-pressure
membrane methods such as nanofiltration and reverse osmosis were developed and fully utilized for
the removal of ECs from wastewater, surface and drinking water while also removing any additional
contaminants present (Onnis etal., 2023). Other membrane tools that have been developed and used
for the elimination of ECs comprise distillation, forward osmosis and electrodialysis. Ionized ECs are
hampered by electrodialysis reversal, while electrostatic, repulsion and sieving are three mechanisms
used in nanofiltration for the removal of ECs. Physiochemical treatment approaches, for example,
adsorption and membrane technology have been identified to have a fair chance of removal of ECs in
wastewater, although more research studies are required for the removal of a large spectrum of ECs
as they need further evaluation and refabrication (Amalina etal., 2023).
The global scarcity of water along with an increase in population over the years has necessitated
the use of wastewater treatment as an alternative source of drinking water (Shehata etal., 2023). This
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214 Detection and Treatment of Emerging Contaminants in Wastewater
process has a high potential for high concentration of the ECs hence, their removal is key if water is
planned for usage in industrial applications and irrigation in farming (du Plessis etal., 2023).
Some of the methods that have been applied to remove the ECs are capable of totally removing
them while others are not effective enough, but this depends on the compound of interest and WWTP.
Several methods have been established for the degradation, reduction, and removal of ECs that would
help mitigate their negative influences the environment (Ng etal., 2023; Tholozan etal., 2023). Basic
wastewater treatment processes usually include the mediation and extraction of soluble and insoluble
contaminants. Several extraction methods such as biological processes, adsorption, membrane-
enhanced oxidation technology and construction of wetlands are ways used to efficiently remove ECs
in wastewater (Ng etal., 2023).
The efficient and cost-effective removal of ECs in different water matrices has proven to be
a difficult challenge, especially in wastewater treatment. In recent years, several techniques have
been established to remove the ECs from wastewater. From an analytical perspective, wastewater
treatment has proven to be difficult due to the multifaceted nature of its matrix, additionally, to that,
its properties vary depending on the inputs to the WWTPs (Coxon & Eaton, 2023). The conventional
WWTPs consist of two treatment stages, namely the primary treatment (application of physiochemical
properties) and secondary treatment (application of activated sludge biological reactor). The efficient
removal of ECs from wastewater generally relies on their nature: physiochemical properties, biological
and chemical form and application process settings.
Traditional municipal WWTPs are not efficiently intended to remove the ECs that exist at low
concentrations such as micrograms/litre (µg/L) and nanogram/litre (ng/L). Advanced technologies
that are affiliated with non-conventional wastewater treatment have been upgraded due to the advance
of new methods. Substantial wastewater treatment expertise may be characterized as advanced
oxidation, biological and physical treatments and phase-changing practices. Conventional techniques
reported for ECs removals generally involved the use of bacteria, both aerobic and anaerobic, but
these systems have proven to be energy-consuming, expensive and have lower removal efficiencies
(Sellaoui etal., 2023).
Sedimentation is a primary treatment process widely used to remove ECs in general conventional
WTTP’s however, their removal is restricted due to the hydrophilic nature of a number of ECs. On
the other hand, the biological process (e.g., ASP) is regarded as the secondary treatment process and
is good at removing the PPCPs through biodegradation partition, biotransformation and adsorption.
Parameters such as sludge age and its adsorption capacity, the way the reactor is designed, nature of the
ECs have a huge impact on effectively eliminating the PPCPs in ASP. Different ECs belonging to one
category can display significant inconsistency in their biodegradability. When the ECs are not entirely
removed in the secondary treatment process this is likely to be attributed to the alteration of ECs into
by-products or metabolites thereby yielding low elimination effectiveness (Jaffari etal., 2023).
Advanced technologies implemented in treatment plants include the following: AOPs, constructed
wetlands (CW), adsorption techniques, hydrolysis processes, chlorination and membrane filtration.
These various treatment processes can be implemented due to the W WTP and the effluent quality
requirements and depending on the specific end-uses. Different AOPs have been applied for the
elimination and degradation of ECs from wastewater, that is, photocatalysis, photo-Fenton, photolysis,
ozonation, ultrasonication, Fenton’s oxidation and solar-driven processes among others (Sellaoui
etal., 2023).
During the sludge treatment process and sludge treatment process, high concentrations of the ECs
present in the particulate and liquid phases are removed via the biodegradation mechanism. The
compound biodegradation mechanism is affected by several factors such as microbial diversity, redox,
toxicity of ECs, hydraulic retention time, temperature, pH, molecular features, potentials, availability
of the ECs to microorganisms and physicochemical properties, amongst others (van den Hurk etal.,
2023). The toxicity of various ECs is mostly affected by the catalytic activity of particular enzymes
subject to their genetic capacities that are degraded by the microorganism. The ECs that do not pose
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215A review of occurrence of emerging contaminants
any threat to the environment are not likely to have an impact on microbial activity. Newly developed
wastewater treatment technologies for the removal of ECs have been categorized as physiochemical
and biological techniques (Jaffari etal., 2023).
11.4.2 Biological methods
Biological treatment that involves the removal or elimination of ECs through biodegradation
mechanisms is extensively used. During the biodegradation process, large ECs molecular compounds
are broken down into small compounds or biomineralized into inorganic compounds such as water and
carbon dioxide using microorganisms such as fungi, bacteria and microalgae among others (Raninga
etal ., 2023). The efficiency rate for the removal or degradation of ECs is affected by different influences
such as the treatment method utilized, physiochemical properties of the target EC species, their
biological persistence and WWTPs operational settings. The common biological treatment techniques
used are generally distributed into two categories, namely conventional and non-conventional. The
categorization of these processes is based on the properties of the wastewater being treated, removal
efficiency, process operation, maintenance and treatment challenges (Coccia & Bontempi, 2023).
One of the important issues that is faced by the wastewater challenges in algal-bioremediation
strategies. The nature and ecotoxicity of wastewater depend on two factors; the type of wastewater
and the source of waste. Procedures such as direct toxicity and water quality assessment, in-vitro and
in-vivo bioassays are utilized to regulate the quality and toxicity of wastewater. Biological methods
are normally applied for the elimination of ECs in wastewater. Biological treatments are generally
differentiated into two groups, namely aerobic and anaerobic processes (Bellas & León, 2023).
Aerobic processes include the application of aerobic bioreactor, membrane bioreactor, sequencing
batch reactor and trickling filter. Whereas anaerobic process examples include the application of
sludge reactors and anaerobic film reactors. The biological treatment process involves the use of
microorganisms for the degradation of the specific target ECs in wastewater into smaller less toxic
molecules or biomineralized into simple organic molecules. The main advantages of biological methods
over physical methods include operational costs and complexities provided that the target analyte(s)
are ready to be biodegradable/oxidized by the microorganisms, the main driver for this technique
is that it effectively destroys the ECs rather than concentrates them. Generally, less information is
documented regarding the biodegradation mechanisms of ECs in environmental conditions (Jatoi
et al., 2023). Implementation of biological methods for the removal of ECs has been proven to be
ineffective in some instances due to numerous non-biodegradable ECs. In addition, most of the
ECs compounds are potentially harmful and can hinder microbial growth which may consequently
hinder the biodegradation process. Hence, wastewater characteristics are crucially important when it
comes to the selection of biological wastewater treatment (Amalina etal., 2023). Biological treatment
processes are time-consuming because of the slow growth rate of the microorganisms used and the
exhausting mineralization periods necessary particularly when fresh microorganism culture is used.
In addition, the application of this treatment method is time-consuming as there is a need for the
cultivation of microorganisms before the degradation process (Ren etal., 2023a, 2023b).
11.4.3 Chemical treatments
Chemical treatment methods possess the capability to attain high elimination efficiency of a targeted
wide variety of ECs as a result of t he chemic al character istics of the wastewater along with t he operating
conditions of WWTPs (Barbosa etal., 2023). Newly developed advanced treatment techniques such
as chemical treatment methods are more efficient and are referred to as chemical oxidation methods
(Coxon & Eaton, 2023).
Treatment techniques based on chemical interaction aim to modify or convert contaminating
pollutants into minimal detrimental effects or biodegradable compounds, and this is achieved by
mineralizing them or transforming them into inorganic compounds that are less hazardous such as
nitrogen, water and carbon dioxide (Zhou etal., 2023).
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216 Detection and Treatment of Emerging Contaminants in Wastewater
These treatment techniques utilize methods such as hydrogen peroxide, ozone, chlorine, oxide-
based-metals and metal-based catalysis coupled with sources like sun, gamma, UV radiation, electric
current and ultrasound among others. There are two types of chemical treatment methods frequently
used and these are conventional oxidation and AOPs (Folorunsho etal., 2023).
11.4.3.1 Conventional oxidation methods
The oxidation treatment process involves the use of oxidizing agents including chlorine and ozone
as the essential methods for the removal of ECs in wastewater (Figure 11.4). During the treatment
process, reactions based on chemical interactions in wastewater can be reactive resulting in the
development of by-products (Kurniawan etal., 2023).
Photolysis, ozonation, the Fenton process and chlorination are dome of some examples of
conventional oxidation methods. Therefore, a careful selection of oxidants to be used is required
before selecting this treatment technique. The utilization of less reactive species such as bromine
and chlorine has been demonstrated to remove the majoring of ECs, studies conducted revealed
high removal efficiencies for ECs such as diclofenac (100%), naproxen (95%), while other ketoprofen,
triclosan, bisphenol A, ibuprofen removal ranged from 38% to 84% (Kurniawan etal., 2023).
Ozone is extensively used in the wastewater treatment process for colour removal, decontamination
properties, reduction of organic pollutants, taste and odour control in drinking water. Ozone is reactive
towards organic pollutants directly or indirectly through interaction with ozone molecules and the free
radicals (made up of hydroxyl OH radicals) that are formed through ozone decomposition (Sewwandi
etal., 2023). The hydroxyl radical is produced during the Fenton reaction process during the reaction of
iron and hydrogen peroxide. Fenton reaction has been advocated for as a viable treatment method for
effluents because of the availability and non-toxicity of iron, but the major concern is the poor removal
efficiency of EC when compared with other oxidation methods and also the production of Fe(OH)3 sludge
(Folorunsho et al ., 2023). The application of the catalyst can help enhance the removal effectiveness
of ECs in Fenton treatment. The compound structures of ECs are damaged/broken down during the
photolysis process and this is caused by the radiation or light during the treatment process. Two photolysis
methods are applied for the degradation of ECs (degradation through photosynthesizers such as hydrogen
peroxide) from wastewater and these are direct and indirect photolysis (Folorunsho etal., 2023).
Ozonation is the most commonly applied method in WWTPs to help enhance the biodegradability
efficiency of ECs. The ozonation method has been proven to efficiently remove all forms of EC
compounds (90–100%) due to its dominant oxidant that reacts with aromatic rings and results in
degrading the EC compound structures. However, the treatment method requires large amounts
of energy, application of ozonation is high-costly and requires immense energy operation (Sellaoui
etal., 2023). Moreover, studies have shown that the activation of free radicals and the formation of
oxidative metabolites pose a major hindrance in this method, and more research work is required to
solve these problems (Abafe etal., 2023). The advantages of using the ionization radiation technique
comprise of good penetration range in water matrix samples such as wastewater, and no requirement
for additional chemicals during the treatment process. Furthermore, it is insensitive to colour and
suspended particles present within wastewater, the uncooperative ECs compounds present within
wastewater can be degraded in situ by reactive species that are created in the course of radiolysis
of water. Disadvantages of this technique include the costly price of radioisotopes used and safety
concerns regarding the use of isotopes (Almazrouei etal., 2023).
11.4.3.2 Advance oxidation processes
Advanced oxidation processes (AOPs) are newly developed removal methods of ECs in wastewater
and provide several advantages over conventional chemical treatment techniques. Research conducted
has reported that the application of improved oxidation techniques resulted in high degradation
efficiencies of ECs and this has been achieved by either using the method alone or coupling it with
other removal methods (Bhattu & Singh, 2023).
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217A review of occurrence of emerging contaminants
Even though some of the chemicals that are used in biological oxidation techniques have proven
challenging to remove, the use of biological oxidation processes for wastewater treatment provides
several advantages. This method can be applied before or subsequently to the biological treatment
process. Removal efficiencies ranging between 80% and 90% were achieved utilizing this technique,
and in some instances above 90% removal efficiencies were achieved by coupling different removal
methods such as coagulat ion, flocculation w ith innovative oxidation methods like sonolysis, ozonation,
UV radiation and electrocatalytic oxidation among others (Ren etal., 2023a, 2023b).
WWTPs and other wastewater management systems that apply AOPs have been described to be
highly effective in the elimination of the ECs. The hydroxyl radicals have been proven to be more
potent oxidizing agents in organic compounds but they are not regarded as catalysts. This chemical
property has been critical in wastewater treatment processes (Ifon etal., 2023).
WWTPs that use AOPs coupled with ozone has been reported to successfully remove ECs. Various
AOPs were recently studied to efficiently remove the ECs from aquatic environments. Researchers
have studied AOPs as an alternative method to effectively remove and degrade the ECs in comparison
with conventional wastewater treatment techniques. The disadvantages emanating from conventional
treat ment techniques are now conquered by the expa nsion of new AOPs like; ultrasonic, photocat alytic,
iron treatment and Fenton processes. To conquer these disadvantages, the use of the electro-Fenton
process has been explored in which hydrogen peroxide is induced in situ via an electrochemical
process under supervised conditions. AOPs have displayed high-efficiency removal of ECs compounds
such as tetracycline, triclosan and acetaminophen among others present in products such as PCPs
and pharmaceuticals which are present in complex wastewater matrices at low concentrations levels
present within the effluent discharge. A major disadvantage in the application of Fenton processes is
high operational and maintenance costs (Bikiaris etal., 2023).
11.4.4 Emerging and hybrid treatment technology
As highlighted, the main aim of the current work is to address and discuss the novelty in the treatment
process that can be used to close the gap of the shortcoming faced by the conventional methods used
to remove the ECs. Some of the disadvantages of the conventional methods; are physical process
including problems of disposing of large amounts of waste after the process, high operational costs,
fouling of the membrane filters, and formation of large amounts of sludge. On the other hand, chemical
process shortcomings include the challenge of removing the microplastics, the formation of sludge in
large quantities, issue of separating the photocatalytic particles in a suspension (Zhou et al., 2023).
The microbiological process faces issues of high costs related to maintenance, precipitates forming
during the process, and failure to function at high levels during cold weather conditions. Based on the
shortcomings mentioned, this work looks at bringing solutions on the potential solution to remove the
ECs in w astewat er. Recent approaches foc us on coupling t he processes , for example, (phy sical + chemical
processes), (physical + biological processes) and (chemical + biological processes). These approaches
are mostly efficient, effective, greener, and environmentally friendly, with low costs for the removal
of ECs in wastewater (Ren etal., 2023a, 2023b). Biodegradation with photocatalysis combined with
biological treatment is an approach that uses a photo catalyst instead of a porous membrane that can
change the pollutants into degradable forms (Richards etal., 2023). Other researchers have started
using the electrochemical approach and there is a need to focus more on these studies and a potential
way to remediate the ECs. For the adsorption approach, the use of nanomaterials has found high
interest. Nanotechnology is a growing field to address the current conventional approaches which have
several drawbacks (Bhattu & Singh, 2023). Some of the nanomaterials; graphene, carbon nanotubes,
and nanomembrane, amongst others are currently being investigated for the remedial options for
ECs in wastewater treatment plants. Recent studies conducted by Bikiaris et al. (2023) revealed that
nano biochar (dendor) is an efficient nanomaterial to remediate ECs in wastewater. Furthermore, the
occurrence of microplastics, pharmaceuticals and personal care products remains a huge global issue,
hence, different approaches investigated include the use of magnetic materials since they are known
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218 Detection and Treatment of Emerging Contaminants in Wastewater
to be flexible and can be easily modified to enhance separation and removal. Generally, during sample
preparations including SPE, magnetic materials can be added forming magnetic solid phase extraction
(MSPE). Research shows that more work needs to be done on utilizing the magnetic materials coupling
with different sample preparations as an alternative approach to remove the ECs in wastewater
(Hawash etal., 2023; Karlsson etal., n.d.).
The occ urrence of emer ging conta minant s (metal ions, r adio nuclei and orga nics) is a global cha llenge
and different nanomaterials are utilized and these include the advanced porous nanomaterials, for
example, porous aromatic framework, covalent organic framework and metal-organic frameworks
(MOFs). These nanomaterials are easily modified making them excellent adsorbents to remove the
ECs (Zhou et al ., 2023). There is a promising approach to synthesizing and fabricating advanced
porous materials and reviewing the adsorption tools between porous materials and environmental
toxins (Krishnan etal., 2023).
The biodegradation process of ECs by photocatalytic process combined with biological treatment
techniques provides numerous benefits such as ecologically friendly, low-cost operation and
maintenance and it is a renewable treatment technique (Gondi et al., 2022). The presence of ECs in
wastewater can also be controlled by applying molecular structured impressed and non-imprinted
polymers. Most EC compounds are degraded by anaerobic digestion processes. The anaerobic
membrane reactor is the current anaerobic digesting technology that possesses high device stability
and offers a large microbial community. In comparison with the conventional anaerobic digestion
approach, the anaerobic bioreactor membrane has better decomposition capabilities for ECs as well
as biogas production (Ulacan et al., 2023).
In summary, the development of new technologies for removing emerging contaminants is
essential for safeguarding water resources and protecting human health. Metal-organic frameworks,
nanotechnology technologies, amongst others, show promise in effectively eliminating a widespread
variety of emerging contaminants from water sources. Additionally, integrating freshwater ecology
with ecotoxicology provides valuable perceptions of the environmental impacts of these pollutants
and aids in the design of effective mitigation strategies.
11.5 CONCLUSION
The treatment of wastewater and reclamation processes has become an important goal in global water
security and sustenance processes, especially in countries that experience severe drought climate
conditions and lack proper WWTPs, while also experiencing expeditious population growth, therefore
driving the demand for safe and clean water even more. Based on the aforementioned reasons, the
monitoring of ECs within water bodies that are used for potable and non-potable activities should be
prioritized to ensure the protection and safety of freshwater ecosystems, which have been proven to
be susceptible to pollution through anthropogenic activities especially taking into consideration the
enormous amounts of the ECs detected in aquatic ecosystems that are not regulated. Additionally, no
ecological and human risk factors associated with these ECs have been established.
Studies reported in research literature have shown that the occurrence of ECs in wastewater
and other water bodies such as pharmaceutical products, nanomaterials, personal care products,
pesticides and herbicides among many more are a global threat to human and animal health as well
the environment as a whole. The presence and transportation pathways of these ECs into aquatic
environments can be explained by various activities such as domestic, hospital, industrial, municipal
and agricultural discharges and by the use of conventional treatment methods used in WWTPs
which have been proven to be inefficient in complete removal of these ECs. Such pollutants are
pervasive in aquatic environments and are seldom detected in drinking water in various countries
globally.
In addition, studies reported also identify that the majority of conventional treatment techniques
for ECs used in WWTPs are inefficient in lowering the concentrations of ECs in effluent discharge to
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219A review of occurrence of emerging contaminants
be below the health and safety required guideline values. Therefore, this highlights the requirement
for modification of existing treatment methods and the development of new innovative methods that
would help improve removal efficiencies of ECs in WWTPs while also reducing their environmental
impact. The presence of ECs at a low concentration within environmental compartments has resulted
in adverse effects and this is due to their toxicity in nature along with frequent occurrence which
impacts human and animal health, especially the aquatic species. Consequently, newly developed
treatment techniques must be incorporated into existing WWTPs and processing systems to try and
combat the ECs pandemic.
The major problems associated with ECs are linked to their adverse effects and the health risks
they pose to human health, animals and the environment. A few of the publications in the literature
associated some of the health effects in humans and animals with the presence of ECs in the
environment they occupy, water and food consumed. The presence of these persistent ECs such as
endocrine disruptors and pharmaceutical compounds highlights the concerns about the reusability
and recyclability of wastewater. The nature, behaviour and complexity of the ECs matrices have
been proven to be more likely to pose negative impacts than single contaminants. This highlights
the significance of further research studies to evaluate the prospective harmful exposure of humans,
animals and the environment to ECs by assessing thei r toxicity. In addit ion, the detection, identification
and quantification of the transformative by-products formed during the treatment process has proven
to be another problem. Moreover, some of these bio-transformed products may be more reactive as
compared to parent compounds therefore posing higher toxicity. Proper analytical methods along with
newly developed detection techniques are required for the identification, quantification, and removal
of EC’ and their transformation products. As reported key issues such as the efficiency of treatment
methods used in WWTPs and environmental health adversities can be addressed through monitoring
the process of WWTPs and affluent discharge. Advances in treatment technologies have proven to be
favourable methods for the elimination of ECs from wastewater. Significant research studies have been
devoted to developing and advancing treatment methodologies for the removal of ECs in wastewater.
Nonetheless, insufficient important knowledge regarding the removal mechanisms of ECs still exists
which indicates a major obstacle in ensuring the safety of reused water from WWTPs.
Chromatographic methods such as HPLC and GC are frequently used techniques for detection,
identification and quantification of ECs present in the environment especially in wastewater at trace
levels. To achieve enhanced sensitivity, accuracy and precision which would help in the quantification
of ECs in trace complex analyte sources such as wastewater, various advanced analytical techniques
have been developed, tested and optimized to ensure high ECs removal efficiency is achieved. In
addition, newly developed fast analysis analytical methods coupled with various sample preparation
techniques such as liquid–liquid microextraction and solid phase microextraction have been developed
to help reduce sample preparation steps and time while also reducing analysis time, eliminating sample
contamination, reducing solvent consumption and costs. The application of these newly developed
techniques for the detection and quantification of ECs in wastewater enabled the possibility of
toxicological evaluations of ECs. Measures to treat and remove ECs in wastewater are still not yet fully
acknowledged, therefore it is important to study and develop new removal techniques. Constructed
wetlands have been identified as low-cost systems that are economically viable and researchers have
been exploring in removing ECs.
Currently, ECs are not regulated as this is demonstrated by the non-existence of threshold limits
discha rge lim its are set by aut horities a nd governing bo dies. Conti nuous discha rge of ECs into t he various
environmental bodies at trace levels poses a risk to human and animal health, and the environment.
Until now, there is a paucity in information concerning the source, transportation, detection, removal,
reactivity and adverse effects of ECs and this has contributed heavily to the limitation of wastewater
quality legislation towards the discharge of ECs in water bodies. ECs have been demonstrated to react
differently in natural environments revealing contrasting ecotoxicological effects that are inadequately
assessed by traditional tests in labs. A holistic approach is necessary and must also be applied when
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220 Detection and Treatment of Emerging Contaminants in Wastewater
environmental assessment studies are conducted, and this should include identifying the impact of
ECs within the environment throughout their complete life cycle and their fate.
Interest in recently developed advanced treatment techniques for ECs such as membrane filtration,
AOPs, adsorption and application of hybrid systems has demonstrated to be more efficient in the
removal of ECs in wastewater. However, various application factors such as performance, costs and
reliability from one process to another. Therefore, there is a requirement for assessment of the adverse
effects of pollution on the removal efficiency of the technique, stability of the treatment mechanism
and microbial organisms used for biological processes. The assessment of these components could
help to produce a standard base from which newly developed treatment techniques can be easily
integrated into existing treatment methods for the removal of ECs in wastewater a nd water purification
processes.
11.6 FUTURE PERSPECTIVE
When developing new methodologies that can be applied in the detection and monitoring of ECs in
water bodies particularly wastewater, sustainability should be prioritized as a necessary characteristic.
However, due to new ECs structures and their metabolites in wastewater at trace level, this results in
obstacles to developing accurate and quick scientific methodologies. Moreover, additional research
is required to refine composition interpretation and the accuracy and sensitivity of the methods. It is
critical to upscale the research pilot-plant to scale real WWTPs that consist of various ECs that are
different and vary in concentrations to clarify the common ramifications of ECs compounds on their
removal rates rather than focusing on experimental work systems that contain one compound used
as a model ECs. A huge amount of newly discovered ECs arise from pollutant compounds that are
undetected during wastewater treatment due to a lack of knowledge and legislation and therefore are
never reported. Therefore, it is imperative to develop new methods for the elimination of ECs and new
legislation for ecotoxicity tests and evaluate various health effects by applying different techniques that
have appropriate termination points for ECs. More exhaustive research work is required which will
fill the knowledge gaps about ECs in conventional WWTPs and newly developed advanced treatment
methods. In addition, research work should incorporate emphasis on WWTPs removal techniques
and the fate of ECs in waste biomass. Integrating nanotechnology science and engineering techniques,
while also improving EC integrity are all crucial components of achieving sufficient elimination of
various ECs in wastewater. Newly developed EC removal studies and techniques should be inclusive of
parameters that affect efficiency such as operational parameters, EC degradation mechanisms, reaction
kinetics and reactor design among others. Evaluation of different treatment methods in real-world
environments and operational scenarios should be implemented rather than focusing on laboratory
batch studies.
In addition, future investigative research assessment studies should focus on clarification of the
predominantly breakdown mechanisms of ECs and the developments of their by-products during
their removal and degradation process. The potential toxicity risk of these by-products towards the
environment should be assessed as some turned out to be far more toxic in comparison with parent
compounds. Furthermore, new and more stringent regulations and policies are required to warrant
the protection, health and safety of our environments.
The application of hybrid systems in W WTPs has gained attention from researchers and
policymakers due to the high removal efficiency of ECs in conducted field studies, although common
biological systems are used mostly in numerous countries globally. The integration of chemical
processes such as AOPs with biological systems still requires more in-depth research, and this could
enhance the suitability and application of hybrid removal technologies. The economic feasibility
of hybrid techniques is a major concern for policymakers, along with the design and operational
parameters for these advanced systems.
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221A review of occurrence of emerging contaminants
Despite all the research progress and technological advancement on removal techniques for ECs in
wastewater, there are still significant limitations that obstruct the progress. The focal point of future
research work should be the following:
• Monitoring of ECs and the transformative by-products because these contaminants are
not assessed due to a paucity of knowledge on their toxicity and persistence within the
environment, therefore, necessitates the development of new protocols and procedures
that will focus on removal and assessment of ECs and their transformative by-products in
wastewater.
• Concentration reduction of ECs from point source-point must be accentuated according to
stricter legislation, public awareness programmes and commanding limited release of ECs to
the environment.
• Explore the application of sustainable ‘green’ removal techniques such as filtration, adsorption
and application of nanotechnology among others at an industrial scale as an efficient and cost-
effective alternative for reduction and removal of ECs concentration from various point sources.
• In-depth research is essential for the incorporation of existing studies on wastewater treatment
techniques with new innovative physical, chemical and biological strategies such as the
application of ultrasound with adsorption and UV radiation for ECs removal.
• Application of effective strategies for selecting suitable treatment methodologies and operation
costs. The selection criteria should include various factors such as water quality and source,
reliabi lity, removal e fficiency of targe ted ECs, flexi bility, envi ronmental c ompatibilit y, ma intenance,
and operating costs among others.
• Advancement in analytical instrumentation provides a possibility to identify and measure
emerging classes of ECs, while new methodologies will help remove these ECs from wastewater
and the environment as a whole.
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© 2024 IWAP. This is an Open Access book chapter dis tributed under the terms of the Creative Commons Attribution License
(CCBY-NC-ND 4.0) w hich permits copying and redistribution for non-commercial purposes with no derivatives, provided the work
is properly cited (ht tps://creativecommons.org/licenses/by-nc-nd/4.0/). The chapter is from the book Detection and Treatment of
Emerging Contaminants in Wastewater, Sartaj Ahmad Bhat, Vineet Kumar, Fusheng Li and Prad eep Verma (Editors).
doi: 10.2166/9781789063752_0227
Chapter 12
Abatement of pharmaceutical
compounds in wastewater using
green nanomaterials: an eco-friendly
alternative to conventional
nanomaterials
Akshay Botle1, Sayli Salgaonkar1, Gayatri Barabde1,2 and Mihir Herlekar1*
1Department of Environmental Science, The Institute of Science, Dr. Homi Bhabha State University, Mumbai 400032, India
2Department of Analytical Chemistry, The Institute of Science, Dr. Homi Bhabha State University, Mumbai 400 032, India
*Corresponding author: tevs.mihir@iscm.ac.in; mihirherlekar1@gmail.com
ABSTRACT
Pharmaceuticals and their remnants have been acknowledged for their ability to save many lives, but they have also
developed a new set of emerging pollutants due to the dif ficulty in treating them in wastewater worldwide. Increased
consumption of drugs has led to adverse impacts on aquatic ecosystems. Even at low levels, these contaminants
cause various problems because of their persistent nature and long-lasting negative effects. Therefore, various
conventional methods such as activated sludge process, chemical precipitation, membrane filtration, ozonation,
adsorption, and photocatalysis have been proposed for their removal. These are limited by high costs, inefficient
removal, the production of toxic materials, and the need for significant investment. Nanotechnology has begun to
explore various effective strategies for treating wastewater with the help of various nanomaterials. Nanomaterials
have been inspected for their potential to eradicate water impurities and improve the effectiveness of conventional
technologies. However, the conventional methods of producing nanomaterials involve the usage of hazardous and
toxic substances, which create additional pollution. Green nanomaterials present plenty of promising avenues
for wastewater treatment and have been recognized to be efficient in providing clean and affordable removal of
pharmaceuticals, with features such as increased surface area, higher reactivity, target specificity, low energ y
and cost consumption, sustainability, improved physical and chemical properties, and effective regeneration. This
has led to the development of innovative trends for creating novel, environmentally friendly nanomaterials for the
removal and degradation of pharmaceutical substances. This paper focuses on these new trends in the development
of greener nanomaterials globally and evaluates their performance for the abatement of pharmaceuticals from
wastewater. The paper concludes with the beneficial aspects of green nanomaterials over conventional technologies
and the future scope of research.
Keywords: wastewater treatment, pharmaceutical compounds, conventional technologies, nanotechnology, green
nanomaterials
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228 Detection and Treatment of Emerging Contaminants in Wastewater
12.1 INTRODUCTION TO EMERGING CONTAMINANTS IN WASTEWATER
12.1.1 Background and significance of the topic
Life originates through water on Earth where there are 2.5% freshwater resources, of which only
1% is accessible. Of the 1% of available freshwater found in the form of rivers, ponds, lakes, and so
on, 30% is underground water and 69% is trapped in glaciers and ice caps. Considering the growing
demand, approximately 80 million people per year add to global freshwater consumption, leading to
an increase of 64 billion cubic meters per year (Elgarahy etal., 2021).
In many industrial sectors, wastewater discharges (effluents) enter the aquatic environment
directly or indirectly. The annual release of water pollutants is estimated to be about 300–400 million
tons (Elgarahy et a l., 2021). Thus, the unaltered release of several newly identified compounds in
the aquatic environment, regardless of their origin, has become a significant concern worldwide,
where typical concentration ranges of these organic contaminants are in parts per billion to parts
per trillion. Such composites are categorized as ‘emerging contaminants (ECs).’ In recent years,
scientists, engineers, and the public have been worried about ‘emerging pollutants’ and their negative
impacts on the living ecosystem (Rout etal., 2021). The United States Department of Defense and the
United States Environmental Protection Agency classify them as potential, likely, or definite health
and environmental concerns (USDoD, 2011; US EPA, 2012). In water bodies, there are several types
of emerging pollutants: pharmaceuticals, surfactants, endocrine disruptive compounds, plasticizers
(Kumar etal., 2022), and others. All these are illustrated in Figure 12.1.
Pharmaceuticals are probably the most concerning emerging contaminants in modern use
(Fernández-López et al., 2016). It is estimated that around 200,000 tons of antibiotics and other
pharmaceutical compounds are produced annually for veterinary and human usage (Khalil et al .,
2021). Antibiotics are extensively practiced in the healthcare division as they possess powerful
antimicrobial and pathogenic actions (Varma et al., 2020). Some of the most regularly found
pharmaceutical-based pollutants are carbamazepine, propranolol, tetracycline, phenytoin, ibuprofen,
estradiol, X-ray contrast, and fenofibric acid. Many of these pharmaceutical compounds found in
wastewater treatment plants (WWTPs) with their uses and disastrous impacts are mentioned in
Table 12.1. Water contaminated with these contaminants is hazardous to humans and the ecosystem.
Moreover, because of their chronic properties, they are difficult to deteriorate (Aguilar-Pérez et al.,
Figure 12.1 Different types of emerging pollutants.
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229Abatement of pharmaceutical compounds in wastewater using green nanomaterials
Table 12.1 Common types of pharmaceuticals found in W WTPs, their uses, and their side ef fects.
Sr.
No.
Pharmaceutical
Compound
Structure Uses Side Effects
1Amphetamine Positive mood, recreational
drug
Insomnia, agitation,
psychotic symptoms
2Atenolol Angina pectoris, acute
myocardial infarction,
hypertension
Headache, confusion,
diarrhea, heart failure,
constipation
3Azithromycin Enteric and urinary tract
infections, respiratory tract
infections
Dizziness, gastrointestinal
upset
4Ciprofloxacin Sexually transmitted
diseases, prostatitis, biliary
tract infections
Vomiting, diarrhea, nausea
5Diclofenac Rheumatic problems, acute
joint, and mild-to-moderate
pain treatment.
Gastrointestinal disorders,
aplastic anemia, disturbed
renal function
6Erythromycin Skin infections, rheumatic
fever, syphilis, intestinal
amebiasis
Abdominal pain, diarrhea,
rash, allergic reaction
(Continued)
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230 Detection and Treatment of Emerging Contaminants in Wastewater
2020). Thus, a rapid increase in antibiotic consumption has been detected in nations including South
Africa, Russia, China, Brazil, and India. In addition to polluting the environment, antibiotic use has
led to the development of resistant microbes to such drugs. Also, many nonsteroidal anti-inflammatory
medicines (NSAIDs) are extremely soluble in water and do not degrade easily; these drugs have been
testified to have an adverse impact on aquatic bodies and humans (Varma etal., 2020).
A large proportion of pharmaceuticals get expelled with feces and urine, entering municipal
WWTPs. During sewage treatment, few composites are removed chemically or biologically while
the rest are adsorbed in solid phases and degraded, but a significant amount of micropollutants are
not eradicated by traditional treatment processes and further treatment is necessary to avert the
discharge of these substances into the environment. Nowadays, a significant route of pharmaceuticals
in habitats is urban wastewater. Clearance of unused pharmaceuticals, veterinary drugs, and feed
additives directly into domestic waste can add to their release into the ecosystem (Gracia-Lor
et al., 2012). In most cases, WWTPs are designed to remove solids and dissolved organics but are
unable to eradicate pharmaceutical compounds effectively; as a result, significant residues remain
in WWTPs (Ramírez-Morales etal., 2020). At present, many methods of remediating pollutants are
costly, nonreplenishable, and environmentally unfriendly and are considered to be causing derivative
pollutants (Azeez etal., 2022).
Advances in nanoscience and nanotechnology have improved wastewater treatment procedures
in recent decades. Compared with traditional treatment techniques, nanotechnology-based pathways
are more effective (Malik etal., 2022). Several fields of research now incorporate nanotechnology as
a front-runner in innovation, especially those that involve creating and modifying bulk materials into
nanoscale (Azeez etal., 2022). Using nanostructured materials to scavenge and eliminate hazardous
water pollutants is becoming more and more crucial because of their unique properties such as
Table 12.1 Common types of pharmaceuticals found in W WTPs, their uses, and their side ef fects (Continued).
Sr.
No.
Pharmaceutical
Compound
Structure Uses Side Effects
7Ibuprofen Gout, dysmenorrhea,
arthritis, osteoarthritis
Kidney diseases,
cardiovascular risks
8Metronidazole Trichomoniasis treatment,
liver abscess
Neurotoxicity,
optic neuropathy,
peripheral neuropathy,
encephalopathy
9Norfloxacin Respiratory, urinary, and
gastrointestinal tract
infections
Hallucinations, insomnia,
central nervous system,
and gastrointestinal tract
illness
10 Tetracycline Acne, cutaneous
sarcoidosis, Kaposi’s
sarcoma, rheumatoid
arthritis, cancer,
cardiovascular diseases
Antibiotic resistance,
allergic reactions, liver, and
dental damage
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231Abatement of pharmaceutical compounds in wastewater using green nanomaterials
unique size, enhanced surface properties, compressibility, exceptional constancy, less intraparticle
diffusion distances, recycling, and remarkable reusability. The effectiveness of nanoparticles (NPs) to
remove pollutants can be increased through fabrication and functionalization. In addition, the use of
flammable substances and harsh compounds for nanomaterial extraction and subsequent processes
poses detrimental concerns. Thus, in light of environmental stewardship and sustainability concerns,
researchers have been inspired to develop environmentally friendly approaches to synthesizing highly
efficient NPs to treat and remove an array of contaminants from the environment (Gautamet a l ., 2 019).
12.1.2 Objectives of the study
This chapter aims to understand the emerging contaminants that are introduced into the environment,
prim arily foc using on phar maceutica l compounds a nd their intr oduction into w astewate r. Fu rther more,
it discusses the sources, types, and toxicology of these compounds, their influence on human health
and the environment, and the conventional approaches to treating these pharmaceutical compounds
in WWTPs. This chapter also provides information on nanomaterials and green nanomaterials used
for treating wastewater, focusing on the use of green nanomaterials for treating pharmaceutical waste
in wastewater.
12.2 PHARMACEUTICAL COMPOUNDS IN WASTEWATER
12.2.1 Sources, composition, types, and toxicology of pharmaceutical compounds
inwastewater
Pharmaceutical products are viewed as an emerging source of pollution by the scientific community
as they have attracted worldwide attention when their production and use have increased in recent
decades. There are about 3000 permitted pharmaceutically active compounds (PhACs) for human
medicines in the European Union. However, global environmental researchers are studying their
probable effects on the environment as they are less understood (Kermia etal., 2016).
In addition to human excretion, unutilized drugs can be flushed directly in toilets, which makes
WWTPs the primary source of these contaminants in aquatic resources (Pereira et al., 2020). The
main sources of pharmaceuticals entering various environmental systems are WWTPs, sites of
manufacturing activities, sewage treatment plants, individual households, large farms, and landfills
(Al-Baldawi etal ., 2021). Global data from 71 countries were evaluated from the year 1996 to 2020 and
adopted from the German Environment Agency–Umweltbundesamt (2023) receiving pharmaceutical
contaminants in WWTPs has been represented in Figure 12.2. Nevertheless, pharmaceuticals are
being used and dispensed by personnel, clinics, and pharmaceutical and agrarian industries, leading
to more continuous environmental entry (Agunbiade & Moodley, 2016). Insignificant bulk drug
manufacturing sites, where wastewater is released, are potential sources of pharmaceuticals (Pereira
etal., 2020). Disposing of outdated medications in garbage, drains, and lavatories is another route.
Medical antibiotics and synthesized hormones used to manage the development and proliferation of
fish breeding and animal rearing are also key contributors to veterinarian medications. Moreover,
routine washing releases pharmaceuticals straight into sewage systems (Al-Baldawi et al., 2021).
Surface and wastewater include sulfonamides, macrolides, and fluoroquinolone antibiotics.
Therapeutic hormones, synthetic versions of plant/animal hormones, alter the endocrine mechanism
and health of animals and humans. Analgesics are often used for pain and inflammation. Analgesics,
notably meprobamate, ibuprofen, acetaminophen, diclofenac, and naproxen, survive in ground and
surface water, and thus, are considered serious environmental contaminants (Tiwari et al., 2017).
Various sources of pharmaceuticals received in WWTPs are illustrated in Figure 12.3.
Effluents from these substances that reach WWTPs are classified as hazardous, nonhazardous,
or chemo waste. There are two sorts of hazardous waste: designated wastes and distinctive wastes.
Pharmaceuticals a re further classified into ‘P’ or ‘U.’ These wastes are regulated due to their corrosivity,
sensitivity, flammability, and toxicity (Gupta etal., 2019). Thus, management of such pharmaceutical
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232 Detection and Treatment of Emerging Contaminants in Wastewater
Figure 12.3 Sources of pharmaceuticals in WWTPs.
Figure 12.2 Pharmaceuticals detected in various WW TPs globally from 1996 to 2020.
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233Abatement of pharmaceutical compounds in wastewater using green nanomaterials
waste derivatives is necessary as they may cause detrimental toxic effects; well-known examples are
the feminization of male fish, the prevention of crustacean molting, and changes in fish behavior
(Huerta etal., 2016).
12.2.2 Impact of pharmaceutical compounds on human health and the environment
Pharmaceuticals may mix and interact in ecosystems, even though most medications are in low
quantities and may not cause damage as separate substances. Pharmaceutical combinations are more
poisonous and ecologically harmful than single substances. Bacteria infect 2 million people annually,
50–70% of which bacteria are antibiotic resistant, out of which antibiotic failure causes 14,000 deaths
(Zhang etal., 2020a).
Pharmaceuticals differ from other pollutants. There are 4000 veterinary and human medications
worldwide, 600 of which have propagated to terrestrial and aquatic ecosystems globally. Pharmaceuticals
may bioaccumulate via trophic chains after entering animals via gills, cuticles, and epidermis. Plants
support food webs and provide net primary production (Néstor & Mariana, 2019). Riaz etal . (2017) tested
levofloxacin, enrofloxacin, ciprofloxacin, and their combination on Triticum aestivum (edible wheat).
The results indicated that antibiotic-treated seedlings have smaller roots and branches. Islas-Flores etal.
(2017) tested the lethality of diclofenac and ibuprofen on Cyprinus carpio, a major farmed teleost fish.
Due to its resistance and ease of care, the fish is often used as a bioindicator in aquatic habitats.
Pharmaceuticals that stay intact after the process develop resistance to deterioration in the
environment. Pharmaceuticals may have solitary, synergistic, or antagonistic effects, including
cancerous or teratogenic, endocrine-disrupting, and antibiotic resistance effects, as well as long-term
harm to living beings (Al-Baldawi etal., 2021). Research discoveries considering the harmful effects
of PhACs and endocrine disruptors have resulted in certain efforts at legislation in the Union of
Europe (Huerta etal., 2016), including diclofenac or the artificial EE2 hormone, which are added
to the list of prioritized drugs by ‘Water Framework Directive’ for ‘the specific objective of assisting
in the identification of suitable procedures to confront the threat posed by such drugs’ (European
Commission, 2013). The US Drinking Water Contaminant Candidate List includes antibiotics and
hormones as PhACs and EDCs (Environmental Protection Agency U.S., 2012). The Global Water
Research Coalition considers atenolol, bezafibrate, diclofenac, erythromycin, carbamazepine,
ibuprofen, naproxen, gemfibrozil, and sulfamethoxazole as paramount drugs to the water cycle (Global
Water Research Coalition, 2008). Thus, due to their health impacts, including nerve and reproductive
toxicity, and intrusion in metabolites, these pollutants have developed a major concern for drinking
water security (Xu etal., 2019).
12.2.3 Conventional methods for treating pharmaceutical compounds in wastewater
Tradition al WW TP procedu res remove macr opollutant s such as susp ended part icles, organ ic pollutant s,
and pathogens but not micropollutants such as stubborn pharmaceutically active chemicals (Rout
etal., 2021). Pharmaceutical residues have been altered by chemical, physical, and biological methods
for years (Ahmed et al., 2017). In coagulation, chemical agents are quickly mixed into wastewater
to disperse pollutants and transform persistent pollutants into completely unstable and precipitable
particulates (Thapa etal ., 2022). Coagulation and flocculation remove turbidity and organic materials
from wastewater. Hydrolytic aluminum and iron salt coagulates are the most common (Zinicovscaia,
2016). Secondary effluents may be cleaned by sedimentation and flotation. Injecting air into wastewater
creates numerous small bubbles, creating floated floc with a lesser density than wastewater (Thapa
et al., 2022). Adsorption moves compounds from aqueous to nonaqueous (solid phase-adsorbent)
phase (Ghazal etal., 2022). Physical and chemical adsorption are major forms of adsorption. Physical
adsorption is reversible and nonselective. Desorbing adsorbate-saturated on activated carbon (AC) is
easy (Thapa etal., 2022). In ozonation, ozone is added to water by bubbling it in a tank via a nozzle.
Ozone directly or indirectly reacts via radical reactions to oxidize toxic compounds (Ghazal et al.,
2022). Catalytic ozonation degrades wastewater organic pollutants. Advanced catalytic ozonation
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234 Detection and Treatment of Emerging Contaminants in Wastewater
may improve ozone utilization and organic pollutant mineralization (Thapa et al., 2022). Most
chemical oxidation procedures efficiently degrade pollutants in wastewater systems to biodegradable
and less hazardous chemicals. Sometimes less reactive species such as chlorine and bromine are used
in WWTPs (Ahmed etal., 2017).
Pharmaceutical wastewater is treated biologically, and the treatment techniques are aerobic
and anaerobic. Microorganisms such as bacteria, microalgae, and fungi biodegrade big molecular
compound pollutants into smaller compounds and even biomineralize compounds into water and
carbon dioxide. Wastewater treatment systems remove ECs by biodegradation. Membrane bioreactor,
sequence batch reactor, and activated sludge are aerobic techniques. Anaerobic techniques include
film reactors, anaerobic digestors, upflow anaerobic sludge blankets, anaerobic filters, and anaerobic
baffled reactors. Although the fraction of contaminants removed by chemical precipitation, primary
settling, sludge absorption, and aerating volatilization, is modest, the bulk of pollutants in wastewater
is eliminated by biological degradation. Using a biological floc with air, this activated sludge procedure
treats sewage and industrial wastewater with bacteria and protozoa. These bacteria are capable of
decomposing organic materials into water, carbon dioxide, and other inorganic chemicals. It is less
expensive to build than advanced oxidation technologies and is more ecologically favorable than
chlorination (Ahmed etal., 2017).
12.2.4 Limitations of conventional methods
The primary drawback of conventional methods is the chemical sludge production during coagulation.
Aluminum-based coagulants can increase residual aluminum in filtered water (Zinicovscaia, 2016).
Temperature, pH, coagulant type, amount, and so on, affect coagulation effectiveness (Gogoi etal.,
2018). AC is costly to produce and regenerate, and its frequent regeneration, replacement, and
discharge are environmental concerns. Nevertheless, the significant amount of organic carbon and
other oxidizable chemicals makes ozonation in WWTPs difficult to deploy as more ozone is needed
to fully treat ordinary sewage. To run an ozonation system, a pharmaceutical facility must purchase a
power supply and transformers. Ozone generators may also minimize residual ozone and boost energy
efficiency by operating intermittently. Intermittent ozonation may limit pharmacological component
elim ination. Phar maceutica l wastewater ozonation pro duces byproduct s that are of ten more hazardous
than the original substances (Ghazal et a l ., 2022). Free chlorine seems to progressively degrade certain
antibiotics, whereas others seem to be more resistant (Gogoi et a l., 2018). Chlorination treatment
produces hazardous byproducts because chlorine interacts with organic substances. As most highly
polar pharmaceuticals cannot be digested by organisms as a source of carbon and may even hinder
their function, activated sludge process-based treatment plants with reduced retention times rarely
eliminate these compounds (Ahmed etal., 2017). Similarly, the major drawbacks of using anaerobic
methods are that they are still uneconomical due to limited flow, membrane fouling, expensive capital,
and operating expenses (Chernicharo etal., 2015).
12.3 NANOMATERIALS FOR WASTEWATER TREATMENT
Micro-engineering, or nanotechnology, manipulates particles under 100 nm. Nanotechnology is
sometimes called the ‘Next Industrial Revolution’ because it will cut power usage, contamination, and
manufacturing costs in industrialized nations. Nanotechnology’s capacity to reduce pollutants may
lead to the most dramatic breakthroughs in environmental protection (Sinha et al., 2020). Adsorption,
photocatalysis, advanced oxidation processes (AOPs), and filtering may eradicate organic pollutants
and pharmacologically active substances using nanomaterials (Nasrollahzadeh etal., 2021).
Treatment of wastewater and cleanup may benefit from nanomaterials’ mechanical qualities,
cost-effectiveness, chemical reactivity, large surface area, and energy efficiency. These well-defined
materials and controlled nanostructures of adequate porosity and size may be effective adsorbents
(Nasrollahzadeh etal., 2021). This section gives information about nanomaterials comprising different
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235Abatement of pharmaceutical compounds in wastewater using green nanomaterials
types, their applications in wastewater treatments, and their advantages over the conventional
process currently being used for the remediation of pharmaceuticals. Thus, numerous categories of
nanomaterials used in treating pharmaceutical wastes are represented in Figure 12.4.
12.3.1 Types of nanomaterials
12.3.1.1 Carbon nanotubes
Carb on nanostr uctures a re extensi vely used as wa stewater na no adsorbents b ecause of thei r abundance,
cost-effectiveness, strong thermal and chemical reliabilities, large active surface areas, outstanding
adsorption capabilities, and nontoxicity (Jain et al., 2021). Carbon nanotubes (CNTs) are excellent
adsorbents with well-defined tube-shaped geometries, enhanced physicochemical couplings, elevated
aspect fractions, greater superficial area, significant sorptive capacities, hydrophobic sides, and readily
changeable facades (Nasrollahzadeh et al., 2021). These CNTs outperform other adsorbents due to
their customizable surface chemistry, chemical inertness, hollowed morphology, greater superficial
area, lighter density, high porosity, and robust engagement with pollutants (Jain etal., 2021).
These qualities make them ideal for wastewater treatment (Jain etal., 2021). CNTs are allotropes
of carbon and may be made from a solitary graphene sheet with a roll-up or from numerous graphene
sheets wrapped up. CNTs outperform activated carbon in sorption due to their elevated aspect
fractions and regulated arrangement of pore size (Cerro-Lopez & Méndez-Rojas, 2019). Kariim etal.
(2020) produced multiwalled CNT adsorbent with nickel-ferrites and activated carbonized from
wood sawdust to sorb levofloxacin and metronidazole from pharmaceutical effluent. The generated
multiwalled CNTs have strong levofloxacin and metronidazole adsorption capabilities.
12.3.1.2 Graphene
Graphene represents one of the most successful upcoming filtering membranes owing to its excellent
selectivity, permeability, cost efficiency, and surface area. Graphene’s simple form and features make
it a popular wastewater treatment pollutant removal material (Ahmed et al., 2022). Graphene oxide
(GO) is a monomolecular graphite film comprising hydroxyl, carboxyl, carbonyl, and epoxide sets (Jain
Figure 12.4 Types of traditional nanoparticles.
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236 Detection and Treatment of Emerging Contaminants in Wastewater
etal., 2021). Despite being costly and difficult in manufacturing, GO is a superior option to graphene
because of its chemical characteristics, which enable it to behave as a barrier with prolonged durability,
which is necessary for a broader variety of processes needing chemical and mechanical capabilities.
Moreover, GO’s efficacy for treating wastewater has already been proved where 90% of ibuprofen was
eradicated in just 180 min using N-dropped 3D Graphene aerogel (Ponnusamy etal., 2021). Antibiotics
may also be successfully removed from wastewater using graphene. It is possible to use graphene to
treat wastewater despite the fact that there are several underlying challenges (Ahmed etal., 2022).
12.3.1.3 Carbon and graphene dots
Carbon quantum dots (Cdots) are sub-ten-nanometer nanopar ticles (NPs) having flat or quasi-spherical
forms, sp2/sp3 hybridized, consisting of heterogeneous functional groups on the surface. Graphene
quantum dots have (<10 nm) dimensions much bigger than their height (<2 nm) (Nasrollahzadeh
et al., 2021). Cdots can detect heavy metals, remove inorganic and organic contaminants, and
photocatalyze contaminants owing to photo-luminescence, semiconductor, antibacterial, and photo-
induced electron transfer properties. Due to their many functional groups and polar moieties, Cdots
may remove hazardous chemicals from wastewater (Ahmed etal., 2022).
Two-dimensional graphene is converted into zero-dimensional graphene quantum dots (GQDs).
GQDs vary from carbon dots as they incorporate graphene lattices less than 100 nm in size and 10
layers thick. GQDs dissolve faster than CNTs. GQDs’ broad edge effect may be adjusted by functional
groups, unlike CNTs’ one-dimensionality (Tian etal., 2018).
12.3.1.4 Zero-valent metals nanoparticles
12.3.1.4.1 Silver nanoparticles
Silver NPs (AgNPs) can cure wastewater because of their high adsorption capacity, antibacterial
characteristics, and sustainable synthesis (Ahmed et a l., 2022). Antimicrobial AgNPs disinfect as
they penetrate microorganisms by changing their membrane structure. It generates cell-damaging free
radicals (Kumar etal., 2021). Junejo etal. (2014) showed amoxicillin-derived AgNPs with catalytic
properties for the degradation of doxycycline, cefditoren, cefixime, ceftriaxone, sodium, and cefdinir
in wastewater.
12.3.1.4.2 Iron nanomaterials
Iron NPs adsorb well. They oxidize and precipitate well but reduce poorly (Kumar et al., 2021).
Bacteria show that zero-valent iron particles are antimicrobial. Staphylococcus aureus, Bacillus
subtilus, Pseudomonas aeruginosa, and Escherichia coli were tested for antiseptic activity (Sadek
etal., 2021). Nanoscale zero-valent iron particles inhibited bacterial development because Fe2+ and
Fe3+ ions damage bacteria’s cell membranes. Zero-valent iron NPs’ growth inhibition boosts their
wastewater treatment capability (Ahmed etal., 2022). Zero-valent iron immobilized in chitosan NPs
removed bisphenol A from pharmaceutical WWTPs (Dehghani etal., 2020).
12.3.1.4.3 Zinc nanoparticles
Zero-valent zinc (ZVZ) has better biodegradability than zero-valent iron; however, wastewater
treatment data are scarce (Ahmed etal., 2022). Zinc has a higher characteristic reduction potential
than iron, thus it removes the pollutant faster (Bokare et al., 2013). ZVZ only abates halogenated
organic molecules such as carbon tetrachloride (Lu etal., 2016). ZVZ’s excellent reductibility and
possible integration with other chemicals may improve its removal efficiency (Ahmed etal., 2022).
12.3.1.5 Metal oxide nanoparticles
12.3.1.5.1 Titanium oxides
Titanium oxide (TiO2) does have a greater bandgap. Consequently, ultraviolet (UV) radiations produce
hydroxyl radicals to ignite titanium oxide NPs. As these hydroxyl radicals injure cells, they impair
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237Abatement of pharmaceutical compounds in wastewater using green nanomaterials
bacteria, fungi, and algae cell structure and function (Kumar etal., 2021). Das et al. (2014) found
68.14% chlorhexidine breakdown in a controlled slurry batch reactor containing TiO2 NPs.
12.3.1.5.2 Iron oxides
Magnetite and maghemite iron oxides have magnetic characteristics that may be used to separate
NPs (Kumar etal., 2021). Magnetic fields may separate absorbent iron NPs. It uses no extra energy,
thus rendering it energy efficient (Ahmed etal ., 2022). Yoon etal . (2017) used methacrylic acid-coated
magnetite NPs to remove carbamazepine and diatrizoate from synthetic wastewater. The amount of
carbamazepine removed was 68.3%, and 61.91% of diatrizoate was removed.
12.3.2 Applications of nanomaterials in wastewater treatment
Nanomaterials are attractive owing to their distinctive chemical and physical characteristics.
Pharmaceutical remediation in wastewater treatment using NPs is recent research. Pharmaceuticals
in wastewater pose a consequential threat to the ecosystem and human health. NPs, nanotubes,
oxides, and so on remove pharmaceuticals from wastewater. These materials may selectively adsorb
or break down pharmaceuticals, making wastewater pharmaceutical removal efficient and effective.
Various applications of using nanomaterials have been discussed in Table 12.2.
12.3.3 Advantages and disadvantages of nanomaterials
Nanomaterials have received a lot of interest during past decades owing to their practical benefits
in various disciplines. These qualities have resulted in the creation of new and better solutions. They
offer various benefits, but they also have certain problems that are mentioned in Table 12.3.
Table 12.2 Applications of nanomaterials in wastewater treatment.
Sr. No. Nanomaterial Used Application References
1Mag netic MWCNTs Used for remediation of tetracycline Zhao etal. (2021)
2TiO2 nanoparticles Used for remediation of meloxicam Nadim etal. (2015)
3Silver-modified TiO2 (Ag/TiO2)
nanoparticles
Used for remediation of
chloramphenicol and tartrazine
Nino-Martinez etal. (2008)
4Sn/Zn/TiO2 photocatalyst Used for remediation of amoxicillin
trihydrate
Mohammadi etal. (2015)
5MWCNT/TiO2/SiO2 composite Used for remediation of
carbamazepine and bisphenol A
Czech and Buda (2015)
6 Multiwalled carbon nanotube Used for remediation of
carbamazepine
Ding etal. (2019)
Table 12.3 Advantages and disadvantages of nanomaterials.
Advantages Disadvantages
• Advanced efficacy
• Enhanced kinetics
• Specific affinities for a particular contaminant
• Improved photocatalysis
• Remarkable microbial activity
• Cost-efficient and eco-friendly
• Large surface-to-volume and functionality ratio
• Active catalytic sites
• Less stable
• Membrane fouling and membrane clogging
• Difficult to implement on a large scale
• Tox ic e ffec t s
• Formation of harmful derivatives on degradation
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238 Detection and Treatment of Emerging Contaminants in Wastewater
12.4 GREEN NANOMATERIALS FOR WASTEWATER TREATMENT
12.4.1 Definition and characteristics of green nanomaterials
Green na notechnology det ermines s ustai nable health a nd environme ntal safe ty. Green nanotech nology
aims to synthesize unique nanomaterials for use in photocatalysis, semiconductors, membranes, and
nanosensors, for pollutant removal and ecological cleanup, and for treatment of wastewater. Greener
nanomaterial synthesis establishes a standard for cleaner, safer, and more ecological nanoproducts.
Green nanomaterials are made from plants, microbes, and other natural resources. Green nanoparticle
synthesis is simpler, cost-effective, more efficient, and ecologically benign than chemical synthesis
(Elgarahy etal., 2021).
Owing to its tiny size, a lot of NPs immediately interact with the medium, altering its reactivity.
Quantum effects in NPs need lower activation energy for chemical reactions. Surface plasmon
resonance in NPs helps detect environmental toxins (Sinha etal., 2020).
12.4.2 Types of green nanomaterials
12.4.2.1 Synthesis of green nanomaterials
Nanopar ticle synthe sis may be top- down or bottom-up. Top-down scaling implies m illing, crushing, and
thermal/laser ablation of thin films or bulk materials. Bottom-up approaches employ NPs, molecules,
atoms, and so on to consciously organize nuclei into superstructures of increasing complexity (Pandit
& Gayatri, 2020).
The initial steps imply the mechanical grinding of a compact material into NPs and stabilizing them
to the desired size. This strategy is hard to narrow. The second technique uses chemical procedures,
including sol–gel, thermolysis, hydrothermal, hydrolysis, and gas phase, to make nanoscale material
from atomic-size material. Laser ablation, aerosol technologies, UV irradiation, and photochemical
reduction produce NPs. Yet, they are costly and produce harmful pollutants. These approaches also
make controlling nanoparticle size, structure, and surface chemistry problematic. Nonetheless, a
bottom-up approach is desirable to manufacture NPs as it initiates with smaller clusters, particles,
and NPs, giving better control over particle shape and size (Devatha & Thalla, 2018). Green synthesis
is the process of creating nanomaterials from plants and plant extracts, microorganisms, fungi, algae,
and so on.
12.4.2.2 Plant and plant extract
Nanomaterials from plant or food leftovers are the most fascinating and ecologically benign kind of
green synthesis. Plant extracts include flavonoids, terpenoids, and phenols, but proteins, glucosides,
and polysaccharides also contribute to nanoparticle production. These bioactive chemicals reduce
and stabilize nanoparticle precursors. This nanoparticle production approach also removes hazardous
substances. The use of heated water extracts bioactive compounds without high-energy methods.
Thus, most manufactured NPs may be used in biomedical applications without harsh reagents. Gold,
silver, and selenium may also produce NPs. Many plant extracts containing reducing, stabilizing, and
capping agents may synthesize AgNPs (Huston etal., 2021). Moulton etal. (2010) produced colloidal
AgNPs using polyphenol-rich tea leaves. Fardsadegh and Jafarizadeh-Malmiri (2019) synthesized
antifungal and antibacterial selenium NPs using aloe vera.
12.4.2.3 Microorganisms
Bacteria used in green nanomaterial manufacturing are with a structured nucleus, unicellular,
possessing cell walls but no organelles. Few bacteria are hazardous but many are harmless and exist
naturally in the body. Escherichia coli and B. subtilis, for instance, are straightforward to nurture and
alter genetically. These traits make bacterial nanoparticle production possible (Huston etal., 2021).
Huston et al. (2021) generated nanomaterials made of sulfides of zinc and lead and oxides of
iron and selenium, using bacterial systems. Tyrosine and tryptophan amino acids in the cell wall
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239Abatement of pharmaceutical compounds in wastewater using green nanomaterials
and cytoplasm of bacteria decrease NPs and stabilize them. Furthermore, ketose and aldose act as
stabilizing/reducing agents. Since amino acids create a protective capping layer in cell walls and
inside cells, they are nonhazardous to mammalian cells (Huston et al ., 2021). Organisms such as
B. licheniformis, P. stutzeri, Acinetobacter calcoaceuticus, B. megatherium, B. amyloliquefaciens,
E. coli, and lactobacillus have been widely used to produce nanomaterials (Prasad etal., 2013). For
instance, Muk herjee (2017) used Microbacterium marinilacus for generating silver, copper, and
magnetic iron oxide and Tripathi et a l . (2014) prepared spherical zinc oxide NPs by using Rhodococcus
pyridinivorans.
12.4.2.4 Fungi
Bioreduction and bioaccumulation make fungi better nanoparticle producers. Fungi’s enzymes and
proteins reduce pollutants by easy hydrolysis. Hydrogenase, nitrate-dependent reductase, and others
help the fungi to bioreduce several contaminants. Fungi produce organic acids, enzymes, proteins,
and polysaccharides that form nanocrystals. Fusarium solani, Coriolus vesicolous, Aspergillus niger,
and A. fumigates mediated bioreduction to create gold and silver NPs. Fungi may absorb metals
via their strong wall binding capacity and intracellular absorption. Fungi decompose extracellular
materials and release enzymes that hydrolyze bulk components to nanostructures. Fungi-mediated
nanoparticle production is cheaper, easier to manage, safer, and easier to handle biomass (Aarthye &
Sureshkumar, 2021). Mukherjee etal. (20 01) found that Verticillium, which causes verticillium wilt,
can generate silver NPs on the cell wall by minimizing aqueous silver nitrate. Ahmad et al. (2005)
and Gericke and Pinches (2006) found that nanospheres and nanorods of gold can be created using
Verticillium luteoalbum and Trichothecium enzymes.
12.4.2.5 Algae
Algae are eukaryotic, photosynthetic, non-plant species. Algae, sometimes termed green biofactories
are cost-effective, critical eukaryotic creatures used in nanotechnology for their low toxicity and
substantial metal bioaccumulation (Huston etal., 2021). Salem etal. (2019) produced AgNPs from
the red algae Portieria hornemannii. Singaravelu etal. (2007) revealed that Sargassum wightii can
make gold-stable NPs.
12.4.3 Advantages of green nanomaterials over conventional nanomaterials
Traditional treatment techniques transport pollutants without decomposing the contaminant to the
environment-benign product. They demand substantial investment, space, and administration (De
Kwaadsteniet e t al . , 2011; Naushad e ta l . , 2013). A n alternative to this is a greener wastewater treatment
method. Green synthesis offers cost-effective manufacturing, energy competence, benign procedures
and byproducts, decreased surplus, and higher pharma and medical use (Hassaan & Hosny, 2018; Ijaz
etal., 2020). Due to their green manufacturing and capacity to reduce environmental toxins, biogenic
NPs are promising materials (Gautam etal., 2019). Bioprepared NPs may absorb contaminants from
aqueous watercourses or degrade organics to benign categories. Biogenic NPs are biorenewable,
sustainable, cheap, and energy-efficient, making them ideal for consumption and manufacturing
wastewater purification methods (Gautam et al., 2019). Thus, the use of natural raw materials, no
toxic chemical involvements, and reduced energy requirements make these green nanomaterials more
efficient than the traditionally available nanomaterials.
12.4.4 Recent research on green nanomaterials for wastewater treatment
Green nanomaterials with their unique properties have spurred an exploration into novel adsorbents.
For environmental applications, a variety of new-generation nanomaterials have been created,
including TiO2, ZnO, oxides of iron, zero-valent metals, and carbon nanotubes (Abouzeid etal ., 2018).
Instances of current trends are highlighted in Table 12.4.
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240 Detection and Treatment of Emerging Contaminants in Wastewater
12.5 ABATEMENT OF PHARMACEUTICAL COMPOUNDS IN WASTEWATER USING GREEN
NANOMATERIALS
12.5.1 Mechanisms of abatement using green nanomaterials
Eco-friendly NPs have been created for effective cleanup and removal of harmful pollutants (Shukla
etal., 2021). Electrostatic interaction adsorption removed sulfamethazine from water using modified
bur cucumber biochar (Letsoalo etal., 2022). Paradis-Tanguay etal. (2019) and Zhang etal. (2020b)
showed high-capacity ibuprofen adsorption employing electrospun ethylene oxide (chitosan)
nanofibers compound and polyacrylic-based Fe3O4− anion exchange resin, where physisorption
removed diclofenac and ibuprofen in these experiments. Hamadeen and Elkhatib (2022) used peels
of pomegranate to prepare activated biochar to remove ciprofloxacin efficiently. Interactions such
as hydrophobic, π–π, electrostatic, and hydrogen bonding dominate ciprofloxacin adsorption by
nanostructured activated biochar. The removal of ciprofloxacin was 89.94% and 84.74% using batch
reactor and packed-bed reactor, respectively.
12.5.2 Factors affecting the efficiency of green nanomaterials in abating pharmaceutical
compounds
Several variables impact nanoparticle creation, characterization, and use. The pH of the state,
temperature, amount of ex tracts, a mount of raw materials, s ize, and methods for nanopar ticle formation
are other essential aspects (Patra & Baek, 2015). Due to surface functional group protonation, the
adsorbent’s surface is positively charged when the solution’s pH is less than the nanocomposite’s pH.
When the nano adsorbent’s surface is negatively charged, the electrostatic interactions between it and
contaminants change, affecting its adsorption capability (Liao eta l ., 2022). For example, ciprofloxacin
adsorption depends on separating media pH (i.e., adsorbent). Nevertheless, increasing pH from 2 to
10 improved ciprofloxacin adsorption with tea waste (Seedher & Sidhu, 2007). Beltrame etal. (2018)
found that ciprofloxacin adsorption on pineapple plant leaf-activated carbon increased to pH 7, then
reduced from pH 8 to pH 9.
Many amoxicillin adsorption processes have been documented, including pH (Anastopoulos etal .,
2020). Amoxicillin adsorption onto many adsorbents increased with pH up to 6 (Jafari etal ., 2018). If
Table 12.4 Recent research on green nanomaterials for wastewater treatment.
Sr.
No.
Nanomaterial Biological
Component
Application in Wastewater References
1nZVI-Cu Pomegranate extract Remediation of tetracycline Gopal etal. (2020)
2Cu Tilia extract residues Remediation of ibuprofen,
diclofenac, and naproxen
Husein etal. (2019)
3Fe3O4Plant extracts of
lemon, black grapes,
and cucumber
Removal of sulfamethoxazole,
piperacillin, tazobactam,
ampicillin tetracycline,
erythromycin, and
trimethoprim
Stan etal. (2017)
4 Activated carbon Olive stones Removal of paracetamol García-Mateos etal. (2015)
5Manganese
nanoparticles
Green tea extract Removal of mitoxantrone He etal. (2021)
6Silver oxide (Ag2O)
nanoparticles
Green leaf extract of
Punica granatum
Removal of sulfamethoxazole El Messaoudi etal. (2022)
7Magnetic Fe3O4
nanoparticles
Excoecaria
cochinchinensis
extract
Rifampicin Cai etal . (2019)
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241Abatement of pharmaceutical compounds in wastewater using green nanomaterials
the solution pH rises over 6, the adsorption range stays near constant (Xing etal., 2013) or declines
(Belhachemi & Djelaila, 2017). With higher pH, amoxicillin’s twofold negative charge and repulsive
forces decrease its adsorption (Anastopoulos et al., 2020). Noirod etal. (2016) found a similar pH
impact on triclosan adsorption onto chitosan. Triclosan adsorption increased with pH and peaked
atpH 3.
Temperature impacts nano adsorbent performance. Adsorption capacity rises with temperature in
endothermic processes and decreases in exothermic processes (Liao etal., 2022). The pyrolytically
generated water hyacinth biochar as adsorbent might decrease ciprofloxacin retention efficiency from
86.05% to 59.75% when the temperature rises from 298 to 338 K (Ngeno etal., 2016). Noirod etal.
(2016) found that adsorption on chitosan for triclosan improved with temperature in the range of
5–65°C owing to increased molecular mobility, sorbent particle kinetic energy, and sorbate–sorbent
collision frequency.
Site and capacity determine the adsorbent dose (Liao et al., 2022). A copper alginate-carbon
nanotube membrane removes tetracycline in 2000 min with 120 mg/g equilibrium adsorption (Zhang
etal., 2022). Adsorbent dosage enhances amoxicillin elimination (Ali et al., 2020). Adsorbent dose
increased tartaric acid-modified wheat grains’ amoxicillin adsorption capability (Boukhelkhal etal.,
2016). Nevertheless, ashes of almond shells, activated carbon from Azolla filiculoides, activated
carbon, and an ultrasound-synthesized magnetic adsorbent from olive kernel had a negative impact
(Balarak e ta l . , 2017; Homem et a l ., 2010; Jafari e ta l . , 2018; Mahmood & Abdulmajeed, 2017). Thus, the
negative effect could be probably because of particle aggregation that reduces overall surface area and
adsorption efficacy at larger doses, reducing adsorption capacity (Mahmood & Abdulmajeed,2017).
12.5.3 Comparison of the effectiveness of green over conventional nanomaterials in abating
pharmaceutical compounds
Nevertheless, chemical and physical techniques of extraction have major disadvantages such as low
output rate, deprived surface development, high cost, elevated energy requirements, and hazardous
reducing agents. Hence, developing an eco-friendly nanoparticle production process is crucial. The
biological synthesis technique is clean and eco-friendly, uses active biological substances such as
enzymes as capping and reducing agents, can be scaled up, and uses less energy (Karunakaran etal.,
2018). Green nanomaterials have various benefits over conventional NPs.
For example, Husein et al. (2019) removed ibuprofen, naproxen, and diclofenac from tilia leaves
using green-synthesized copper NPs. The amount of ibuprofen, naproxen, and diclofenac removed
was 74.4%, 86.9%, and 91.4%, respectively. Kim etal. (2020) found that maple leaf biochar removed
tetracycline at 407.3 mg/g, making it a more effective adsorbent than conventional ones. Weng
etal. (2018) made green synthetic Fe3O4 magnetite NPs from Euphorbia cochinchinensis extract to
remove doxorubicin hydrochloride, an anti-cancer medication. Green NPs at 303 K removed 80.2%
doxorubicin. Debnath e t a l . (2020) employed P. aeruginosa bact eria to sy nthesize zi rconia nanopa rticles
for wastewater tetracycline bioremediation. Zirconia nanoparticles have a Langmuir isotherm model-
calculated maximal tetracycline adsorption capacity of 526.32 mg/g. Zirconia nanoparticles may be
used to reduce wastewater tetracycline contamination. Ahmed et al . (2023) used green tea leaves
to make an iron–copper nanocomposite on alginate limestone. The iron–copper nanocomposite on
alginate limestone adsorbs ciprofloxacin and levofloxacin from contaminated media. Kinetic and
isotherm models calculated adsorption parameters. This innovative abatement approach removed
ciprofloxacin and levofloxacin at 20 ppm, 97.3%, and 10 ppm, 100%, respectively. Abdel-Aziz et al.
(2019) produced bimetallic nano zero-valent Fe/Cu via green technology using Ficus benjamina leaves
to remove carbamazepine. Carbamazepine elimination was 95% at 0.4 g/L at pH 5 in 20 min. The
Freundlich and Langmuir adsorption isotherms showed that carbamazepine elimination was better
than with typical nanomaterials. Misra et al. (2018) tested green-synthesized superparamagnetic
iron oxide nanoparticles for carbamazepine cleanup. This work generated magnetic nano sorbents
by coprecipitation employing Colocasia esculenta corms, piper bettle leaves, and Nelumbo nucifera
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242 Detection and Treatment of Emerging Contaminants in Wastewater
stalk extracts to modify nanoparticle surfaces. N. nucifera extract-coated nanoparticles had the best
removal effectiveness (52% at 5 ppm). Hoslett etal. (2021) made tetracycline-removing biochar from
food and garden waste, which showed tetracycline removal up to 9.45 mg/g.
12.5.4 Future prospects and challenges of using green nanomaterials for abating
pharmaceutical compounds
Nanotechnology is promising in medicine, energy, and the environment. Green nanomaterials for
pharmaceutical chemical abatement seem promising. These materials may be cost-effective and
efficient. Green nanoparticles are less costly and energy-intensive than typical wastewater treatment
processes. Green nanoparticles may also be employed in domestic wastewater treatment and large-
scale industrial activities. Green nanoparticles could potentially be used in wastewater treatment
systems to eliminate pharmaceutical chemicals. Green nanoparticles may increase pharmaceutical
chemical removal in these systems, minimizing their environmental effect.
Green nanomaterials for pharmaceutical compound abatement have some drawbacks. It struggles
with raw ingredients, reaction circumstances, product quality, and application. These issues hinder
manufacturing and large-scale usage of green nanomaterial (Guan et al., 2022). Researchers found
that local plants are suitable for green NP production. These studies imply that native plants may be
fully used, although global nanomaterial manufacturing is problematic (Turunc et al., 2017). Some
greener synthetic processes need high temperatures and long synthesizing times, which may affect the
environment. Although employing ecologically friendly chemicals, the procedure does not necessarily
follow sustainable synthesis principles (Muthuvel etal., 2020). A dearth of knowledge of the synthesis
pathway makes it hard to find chemical reactions that demonstrate green synthesis (Kora & Rastogi,
2016). Different extracts yield nanoparticles of varied shapes and sizes, and quality assessment is
inadequate. Current sources say that particle diameter fluctuates widely, making green technology
unsuited for large-scale production and particle size control difficult throughout the manufacturing
process (Chahardoli etal ., 2018). Green nanomaterials could be harmful. If mishandled, these natural
resources may harm the environment and human health. Before mass-producing green nanomaterials,
their toxicity must be assessed.
12.6 CONCLUSION
12.6.1 Recommendations for future research
To ensure considerable water quality for drinking while also eliminating micropollutants, novel
sophisticated water systems must be adopted. Flexible and diverse water treatment technologies
must be employed to improve industrial production processes. One of the primary advantages of
nanomaterials over traditional water-based approaches is their capacity to comprise a wide range of
characteristics in different systems, such as membranes made of nanocomposite that allow for particle
retention as well as pollutant removal. In addition, because of their unique qualities, such as a large
surface area, nanoparticles improve the effectiveness of processes. At this moment, it is essential to call
attention to a handful of critical disadvantages. Substances enhanced by NPs, for example, integrated
into or placed on their surface, have the capacity to be hazardous since NPs may be discharged into
the environment and progressively accumulate. Numerous local and global standards and legislation
are being developed to mitigate health risks. The main technical constraint of nano-engineered
water treatment techniques is that it is barely adaptable to huge-scale operations and is occasionally
cost-competitive with traditional treatment methods. Cleaner and more plentiful nano-engineered
materials, on the other hand, offer huge promise for progress in the coming decades, especially for
decentralized treatment facilities. Before these green-synthesized nanocatalysts and nanomaterials
may be deployed at industrial and commercial sizes, additional research into their sustainability and
toxicity is necessary. Although the production of these nanomaterials is efficient and sustainable,
certain vital and challenging aspects, such as the impact of reactions and instability problems,
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243Abatement of pharmaceutical compounds in wastewater using green nanomaterials
must be investigated and optimized, as these variables can alter the behavior of nanomaterials,
their morphologies, and their efficacy in removing pollutants. More research is required to identify
novel nanohybrids and multifunctional nanomaterials that can be used in practical applications.
Effectiveness concerns and remedial performance assessments are often created on laboratory scales,
replicating the various degrees of genuine exposure settings, but realistic environmental conditions
must be explored and assessed.
12.6.2 Final thoughts and implications for practice
Pharmaceutical compounds in wastewater are becoming a growing public health and environmental
concern. Nanomaterials have the potential to enhance wastewater treatment. Green nanoparticles are
thought to be more environmentally friendly and sustainable than regular nanomaterials. In summary,
there is enormous potential in the application of ecologically benign nanomaterials for pharmaceutical
chemical abatement in WWTPs. However, further research is needed not only to fully appreciate the
processes in use, but also to overcome the challenges associated with their manufacture, capacity, and
affordability.
12.6.3 Summary of the study
Using green-synthesized nanomaterials, pharmaceuticals may be effectively eliminated at an affordable
cost. Additional studies should concentrate on enhanci ng the economic feasibility of these nanoparticles
and analyzing their interaction dynamics in water treatment systems since low production costs are
crucial for the broad usage of these nanomaterials in wastewater treatment. Subsequently, it is also vital
to do study on their possible harm to human health and the environment; comprehensive analyses are
necessary to ensure that they are safe for use. In addition to eliminating the major drawbacks of existing
technologies, nanotechnology-enabled wastewater treatment systems should also offer innovative
wastewater treatment solutions that allow non-conventional water resources for water supply to be
economically recovered and grown. The potential for the use of green-synthesized nanomaterials for
remediation is highly exciting, but serious problems concerning toxicity, biosafety, and the mechanistic
characteristics of these materials need to be addressed completely and systematically.
ACKNOWLEDGMENT
We are thankful to Nida Sarfaraz for copyediting and proofreading the manuscript.
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ISBN: 9781789063745 (paperback)
ISBN: 9781789063752 (ebook)
ISBN: 9781789063769 (ePub)
Detection and Treatment of Emerging Contaminants in Wastewater Edited by Sartaj Ahmad Bhat, Vineet Kumar,
Fusheng Li and Pradeep Verma
Detection and Treatment of Emerging Contaminants in Wastewater addresses the critical and
pressing need for effective strategies to detect and treat emerging contaminants, thereby
mitigating risks associated with their presence in wastewater. This comprehensive book
features contributions from prominent experts in the field of wastewater, providing an
up-to-date and in-depth collection of chapters dedicated to tackling this pressing issue.
Highlights:
• The book serves as an invaluable resource for identifying, assessing, and comprehensively
addressing emerging contaminants in wastewater and/or sludges. It delves into the
assessment, mitigation, and treatment of various contaminants, including microplastics,
antibiotic-resistant genes, pharmaceuticals, personal care products and industrial chemicals.
• An exploration of the behavior of microplastics in different wastewater treatment plants and
their accumulation in sludge, shedding light on their potential impact on the environment.
• An introduction to the key mechanisms for the removal of emerging pollutants from sludge
through fungal-mediated processes, offering innovative solutions for effective treatment.
• An investigation into the fate and behavior of pharmaceutically-active compounds in
wastewater, along with their potential environmental impacts. Additionally, accurate
quantification procedures for these compounds are discussed.
• The book covers new trends in the development of greener nanomaterials, evaluating their
performance for abating emerging contaminants from wastewater.
With its comprehensive insights and diverse perspectives, this book is an essential guide
for researchers, professionals, and policymakers engaged in wastewater management and
environmental protection. The practical solutions and scientific knowledge presented herein
will contribute significantly to safeguarding our water resources and ensuring a cleaner and
healthier future.
Detection and
Treatment of Emerging
Contaminants
in Wastewater
Edited by Sartaj Ahmad Bhat, Vineet Kumar,
Fusheng Li and Pradeep Verma
Detection and Treatment_layout_1.0.indd 1Detection and Treatment_layout_1.0.indd 1 26/01/2024 12:4826/01/2024 12:48
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