Organic Micropollutants in Aquatic and Terrestrial Environments 3031489764, 9783031489761

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Rahul Bhadouria · Sachchidanand Tripathi · Pardeep Singh · Rishikesh Singh · Harminder Pal Singh   Editors

Organic Micropollutants in Aquatic and Terrestrial Environments

Organic Micropollutants in Aquatic and Terrestrial Environments

Rahul Bhadouria • Sachchidanand Tripathi • Pardeep Singh • Rishikesh Singh • Harminder Pal Singh Editors

Organic Micropollutants in Aquatic and Terrestrial Environments

Editors Rahul Bhadouria Department of Environmental Studies, Delhi College of Arts and Commerce University of Delhi New Delhi, India

Sachchidanand Tripathi Department of Botany, Deen Dayal Upadhyaya College University of Delhi New Delhi, India

Pardeep Singh Department of Environmental Studies, PGDAV College University of Delhi New Delhi, India

Rishikesh Singh Amity School of Earth & Environmental Sciences Amity University Punjab Mohali, India

Harminder Pal Singh Department of Environment Studies Panjab University Chandigarh, India

ISBN 978-3-031-48977-8 ISBN 978-3-031-48976-1 https://doi.org/10.1007/978-3-031-48977-8

(eBook)

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland Printed on acid-free paper.

Preface

Organic micropollutants (OMPs) such as pharmaceutically-active compounds, cosmetics, chemicals interfering with endocrine functioning, pesticidal compounds, industrial chemicals, by-products of disinfectants, additives, common preservatives, perfluorinated compounds, different classes of detergents, surfactants, flame retardants, plasticisers, and their transformation products, and micro-plastics are some of the most common types of OMPs prevalent in the environment. Their prevalence, fate, and eco-toxicological impact on the environment are a relatively new concern for the society. OMPs are currently receiving more attention as researchers are trying to figure out what happens to them and how they affect the environment. Hundreds of OMPs and their metabolites have been derived from natural sources across the world. Even at low concentrations, the continual discharge of these contaminants without due regulatory measures may pose serious challenges to the environment. Many organic micropollutants’ environmental fates, as well as their eco-toxicological potential, have been documented recently. The uncertain fate and lack of systematic scientific data regarding OMPs may become a grave concern for human health and the environment. Long-term exposure to OMPs has been reported to accelerate the pervasiveness of diabetes, obesity, hormonal imbalances, cancer, cardiovascular, and reproductive ailments in humans. The longevity of these OMPs in the environment is determined by a variety of mechanisms, including bioaccumulation and bio-magnification, and their complicated structure makes them difficult to degrade or change dynamically. While acute toxicity from OMPs is uncommon at ambient concentrations, persistent exposures can harm ecosystem biotic components. Organic micropollutants (OMPs) are a set of words used to describe a category of substances that are not addressed by current water quality legal frameworks due to their occurrence in low quantities or non-detectability through common analytical methods, although having a great potential to affect the environment and ecosystems. There are reports of contamination of OMPs in municipal water supplies in many developing countries which is certainly a great concern and need to be properly dealt with. The effects of OMPs in aquatic environment are not much v

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known yet, however, there are evidences of their acute and chronic impact on the biota inhabiting these ecosystems. Fish early life stage-tests support awareness of detrimental OMPs’ effects on lives. Bioaccumulation, toxicity, and resistance to degradation are reasons for potential risks of OMPs. Often the conventional wastewater treatment plants are not efficiently designed to remove OMPs at low concentration, and therefore, show their limitation in taking care of these potentially hazardous compounds. OMPs like polychlorinated dibenzodioxins and furans, polychlorinated biphenyls, polybrominated diphenyl ethers, perfluoroalkyl substances, and polycyclic aromatic hydrocarbons have shown their adverse effects on human and other organisms. Many of the persistent OMPs are halogenated and characterised by a carbon–chlorine bond which is very stable in nature and prevents persistent OMPs from persistent organic pollutants’ (POPs) biological, chemical, and photolytic degradation. Due to their semi-volatile nature, they can be transported to longer distances through wind and sea waters even in low concentrations across the world. Persistent OMPs are less water soluble and being high lipophilic they can cross the phospholipid bilayer and accumulate in living organisms, therefore, increasing the threat of bioaccumulation and bio-magnification in the trophic chain. This warrants some necessary preventive measures to be taken by concerned institutions, scientists, and authorities. Concrete and objective methodologies to generate data on OMPs application, environmental fate, and mobility must be developed to assess probable risks and hazards of OMPs and their metabolites. This book ensembles knowledge on the genesis and fates of OMPs, including their environmental cycling/transformation process, toxicity to organisms, impacts on various ecosystems, and remediation opportunities. The book has 16 chapters which are contributed by authors originating from 10 countries, viz., Algeria, China, India, Korea, Nigeria, Poland, Sudan, the United Arab Emirates (UAE), Ukraine, the United States of America (USA). All the 16 chapters have been further divided into five distinct themes/parts: 1. Organic micropollutants: Origin and occurrence in the environment (Chapters First to Third); 2. Effects of organic micropollutants on the environment and human health (Chapters Fourth to Sixth); 3. Assessment and detection methodologies for organic micropollutants (Chapters Seventh to Ninth); 4. Treatment and remediation approaches for organic micropollutants (Chapters Tenth to Fifteenth); 5. Organic micropollutants in the environment: Concluding remarks (Chapter Sixteenth). The opening chapter of the book, i.e., First Chapter, entitled ‘Organic micropollutants in environment: Origin and occurrence’ by Amar Jyoti Kalita et al. provides a better understanding of origin, types, occurrences, and adverse effects of OMPs on the environment and human health. Second Chapter, ‘Contamination of aquatic ecosystem with pharmaceutical and personal care micropollutants’ by Siddhant Srivastava and Swati Sachdev, provides details on the contamination of aquatic ecosystems with pharmaceuticals and personal care products micropollutants, discusses their impact on humans and the environment, and delineates the role of bioremediation in their management.

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Third Chapter, ‘Organic micropollutants in the urban soils: Technological advances and management concerns’ by Ravneet Kaur et al., gives a detailed review on the types of OMPs, their occurrence and sources of production as well as their effects on different life forms. Fourth Chapter, ‘Assessment of environmental pollutants for their toxicological effects of human and animal health’ by MVNL Chaitanya et al., assessed the important environmental pollutants and their biological or toxicological impacts on human and animal health. Fifth Chapter, ‘Organic micropollutants and their effects on the environment and human health’ by Archna Kumar et al., attempts to analyse the types of micropollutants, their sources, pathways, fate, distribution, and possible remediation in the environment. Sixth Chapter, ‘Occurrence and toxicity of organic microcontaminants in agricultural perspective: An overview’ by Hardik Giri Gosai et al., provided an overview on prevalence and concentration patterns of organic micropollutants in agricultural fields, by giving emphasis on their routes of transfer to the agroecosystems and associated control measures. Seventh Chapter, ‘Comprehensive methods for the analysis of organic micropollutants’ by Soumeia Zeghoud et al., described the numerous analytical methods used for various OMPs. Authors of this chapter also elaborated the challenges in analysing these pollutants and evaluates the potential of each instrument in the analytical process. Eighth Chapter, ‘Methodologies for the detection and remediation of organic micropollutants in terrestrial ecosystems’ by Jatinder Singh, provided a significant insight into the technology used for the removal of OMPs and comprehensively reviewed the current removal methods, mechanisms, comparisons of methods with their advantages and disadvantages as well as future outlooks and recommendations. Ninth Chapter, ‘Assessment, obstacles, and risk communication for organic micropollutants in the urban water’ by Jaskiran Kaur, discussed the possible types and updated sources of organic pollutants in urban water cycle. Authors of this chapter also discussed about the impacts of organic micropollutants on the biotic as well as abiotic components of the ecosystem. Tenth Chapter, ‘Organic micropollutants in the freshwater ecosystem: Environmental effects, potential treatments and limitations’ by Asha Sharma et al., provided an overview on the detection of OMPs and concentration in a freshwater ecosystem and how these OMPs are transported to the freshwater ecosystem as well as the environmental impacts of OMPs along with various treatment techniques. Eleventh Chapter, ‘Organic micropollutants in wastewaters: Advances in sustainable management and treatment methods’ by Barbara Sawicka et al., deals with the advances in sustainable management and treatment methods of OMPs in wastewater ecosystem. Twelfth Chapter, ‘Organic micropollutants in the environment: Ecotoxicity potential and bioremediation approaches’ by Shalini Gupta, discussed the exposure and fate of these pollutants among invertebrates, vertebrates, plants, crops, and

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humans. The potential risk factors, abatement of OMPs through the bioremediation process, and future strategy have also been highlighted in this chapter. Thirteenth Chapter, ‘Organic micropollutants in agricultural system: Eco-toxicity, risk-assessment, and detection methods’ by Archna Kumar et al., elaborated the transport of pesticides in the environment and their detrimental effects on human health as well as flora, fauna, soil, water, etc. The authors also provided existing methods of detection, identification, quantification, and remediation of OMPs. Fourteenth Chapter, ‘Process of removing organic micropollutants using advanced oxidation techniques’ by Harleen Kaur et al., highlighted the working mechanisms and benefits of different advanced oxidation processes (AOPs) such as Ozonation, Fenton-based AOPs, etc. used to lower micropollutant levels. Further research into these technologies could prove valuable for environmental remediation. The penultimate chapter of the book (Fifteenth Chapter), entitled ‘Biodegradation pathways of hexachlorocyclohexane (HCH): A case study’ by Divya Agarwal et al., provided brief insight on biodegradation pathways of hexachlorocyclohexane. The ultimate chapter of the book, i.e., Sixteenth Chapter, entitled ‘Fate of organic micropollutants in aquatic environment: Policies and regulatory measures’, by Abdulhamid Yusuf et al. addresses the sources and the fate of OMPs in aquatic environments, including sorption, biodegradation, and photodegradation. Authors also reviewed the various analytical methodologies employed for the identification and quantification of OMPs in aquatic ecosystems. They also emphasised on more comprehensive field and laboratory research for the development of more effective and sensitive treatment technologies, and the integration of chemical and biological approaches to assess the potential risks of OMPs. Overall, while going through the book, readers will find a valuable discussion on the current contamination status of terrestrial and aquatic ecosystems by pharmaceutical and personal care micropollutants, the latest methodologies for analysing organic micropollutants, and a case study on the biodegradation pathways of hexachlorocyclohexane (HCH). Given its breadth, this book is a useful resource for scientists, researchers, policymakers, and anyone concerned about the ecological and human health impacts of organic micropollutants. New Delhi, India New Delhi, India New Delhi, India Mohali, India Chandigarh, India

Rahul Bhadouria Sachchidanand Tripathi Pardeep Singh Rishikesh Singh Harminder Pal Singh

Contents

Part I

Organic Micropollutants: Origin and Occurrence in the Environment

Organic Micropollutants in Environment: Origin and Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Amar Jyoti Kalita, Jyotirmoy Sarma, Akangkhya Hazarika, Srishti Bardhan, Nabanita Hazarika, Panchami Borppujari, Debajit Kalita, and Sanchayita Rajkhowa Contamination of Aquatic Ecosystem with Pharmaceutical and Personal Care Micropollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Siddhant Srivastava and Swati Sachdev Organic Micropollutants in the Urban Soils: Technological Advances and Management Concerns . . . . . . . . . . . . . . . . . . . . . . . . . . Ravneet Kaur, Harleen Kaur, Swapnil Singh, Neetu Jagota, Ashutosh Sharma, and Ashish Sharma Part II

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Effects of Organic Micropollutants on the Environment and Human Health

Assessment of Environmental Pollutants for Their Toxicological Effects of Human and Animal Health . . . . . . . . . . . . . . . . . . . . . . . . . . . M. V. N. L. Chaitanya, Smriti Arora, Rashmi Saxena Pal, Heyam Saad Ali, B. M. El Haj, and Rajan Logesh Organic Micropollutants and Their Effects on the Environment and Human Health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Archna Kumar, Deepika, Dhruv Tyagi, Tarkeshwar, and Kapinder

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Occurrence and Toxicity of Organic Microcontaminants in Agricultural Perspective: An Overview . . . . . . . . . . . . . . . . . . . . . . . . . 107 Hardik Giri Gosai, Foram Jadeja, Asha Sharma, and Shilpi Jain ix

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Contents

Assessment and Detection Methodologies for Organic Micropollutants

Comprehensive Methods for the Analysis of Organic Micro pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129 Soumeia Zeghoud, Hadia Hemmami, Ilham Ben Amor, Bachir Ben Seghir, Abdelkrim Rebiai, and Imane Kouadri Methodologies for the Detection and Remediation of Organic Micropollutants in Terrestrial Ecosystems . . . . . . . . . . . . . . . . . . . . . . . 159 Jatinder Singh Randhawa Assessment, Obstacles, and Risk Communication for Organic Micropollutants in the Urban Water . . . . . . . . . . . . . . . . . . . . . . . . . . . 181 Jaskiran Kaur Part IV

Treatment and Remediation Approaches for Organic Micropollutants

Organic Micropollutants in the Freshwater Ecosystem: Environmental Effects, Potential Treatments, and Limitations . . . . . . . . 203 Asha Sharma, Foram Jadeja, Hardik Giri Gosai, and Shilpi Jain Organic Micropollutants in Wastewaters: Advances in Sustainable Management and Treatment Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 225 Barbara Sawicka, Mohammed Messaoudi, Viola Vambol, Sergij Vambol, Nadjet Osmani, Wafa Zahnit, Dominika Skiba, Ilham Ben Amor, Bachir Ben Seghir, and Abdelkrim Rebiai Organic Micropollutants in the Environment: Ecotoxicity Potential and Bioremediation Approaches . . . . . . . . . . . . . . . . . . . . . . . 249 Shalini Gupta Organic Micropollutants in Agricultural System: Ecotoxicity, Risk Assessment and Detection Methods . . . . . . . . . . . . . . . . . . . . . . . . 265 Archna Kumar, Deepika, Dhruv Tyagi, Tarkeshwar, and Kapinder Process of Removing Organic Micropollutants Using Advanced Oxidation Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295 Harleen Kaur, Ravneet Kaur, Neetu Jagota, Swapnil Singh, Ashutosh Sharma, and Ashish Sharma Biodegradation Pathways of Hexachlorocyclohexane (HCH): A Case Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315 Divya Agarwal, Anil K. Gupta, and Mohammad Yunus

Contents

Part V

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Organic Micropollutants in the Environment: Concluding Remarks

Fate of Organic Micropollutants in Aquatic Environment: Policies and Regulatory Measures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331 Abdulhamid Yusuf, Fidelis Odedishemi Ajibade, Temitope Fausat Ajibade, Ogunniran Blessing Ifeoluwa, Kayode Hassan Lasisi, Nathaniel Azibuike Nwogwu, Bashir Adelodun, Pankaj Kumar, Ifeoluwa Funmilola Omotade, and Christopher Oluwakunmi Akinbile

Part I

Organic Micropollutants: Origin and Occurrence in the Environment

Organic Micropollutants in Environment: Origin and Occurrence Amar Jyoti Kalita, Jyotirmoy Sarma, Akangkhya Hazarika, Srishti Bardhan, Nabanita Hazarika, Panchami Borppujari, Debajit Kalita, and Sanchayita Rajkhowa

Abstract It is relatively recent in the history of human development that societies are facing the challenge of figuring out the fate and occurrence of organic micropollutants (OMPs) in the environment as well as their ecological significance. When these pollutants are discharged continuously without any regulatory measures, even at low concentrations, they may pose an environmental threat. In recent studies, many OMPs have been analyzed for their environmental fates and ecotoxicological effects. Chronic exposure to OMPs may cause ecosystem damage, but acute toxicity is unlikely at environmental concentrations. The purpose of this book chapter is to discuss the role played by OMPs including their origin, types, occurrences, and adverse effects on the environment and human health. Detection and analysis of OMPs in the environment will begin with the development of sensitive and robust methods. If proper measures are not taken by the relevant authorities and scientific community, unwanted consequences may result. Keywords Biotransformation · Detection · Fate · Pollutant metabolism · Regulatory measures · Water resources

A. J. Kalita Department of Chemistry, Dibrugarh University, Dibrugarh, Assam, India J. Sarma Department of Chemistry, Assam Don Bosco University, Sonapur, Assam, India e-mail: [email protected] A. Hazarika · D. Kalita Department of Microbiology, The Assam Royal Global University, Kamrup (M), Assam, India S. Bardhan Department of Chemistry, The Assam Royal Global University, Guwahati, Assam, India N. Hazarika Department of Social Work, Royal Global University, Guwahati, Assam, India P. Borppujari Department of Biotechnology, Sikkim University, Gangtok, Sikkim, India S. Rajkhowa (✉) Department of Chemistry, Haflong Government College, Dima Hasao, Assam, India © The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 R. Bhadouria et al. (eds.), Organic Micropollutants in Aquatic and Terrestrial Environments, https://doi.org/10.1007/978-3-031-48977-8_1

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1 Introduction In the past decade, multiple human activities, including agriculture, industry, transport, and urbanization, have resulted in adverse consequences for the world. As living standards rise and consumer demand increases, the water and air are becoming polluted with chemicals, nutrients, industrial effluents, oil spills, and many more along with greenhouse gases, NOx, SO2, and dust. Using disposable goods and nonbiodegradable materials, and pesticides, and dumping hazardous wastes and sludge on the soil contaminate the environment, and these are referred to as micropollutants (MPs) (Gavrilescu 2010). There are several obstacles in identifying and quantifying these micropollutants, including “transportation, handling, and instrumentation” limitations. Analyzing micropollutants is commonly expensive, and most studies quantify pre-selected analytes rather than identify all the compounds in natural matrices (Reyes et al. 2021). A wide range of studies has suggested that the presence of pharmaceutic agents in the surroundings, particularly in soil and water, can adversely affect wildlife, including fish, birds, insects, and the wider ecosystem, which may lead to antimicrobial resistance (Wilkinson et al. 2022). Between 1930 and 2000, there was a massive increase of one million tons of anthropogenic chemicals produced globally, going from 1 to 400 million tons of anthropogenic chemicals each year (Özkara and Akyil 2018). The organic micropollutants (OMP) which are very tenacious can be distinguished in amounts starting from a ng/L to g/L in the environment. MPs are tiny, practically inconspicuous, components of goods that are used on a regular basis, such as insecticides, medications, cosmetics, fertilizers, and industrial chemicals. Contrary to microplastics, the majority of micropollutants are difficult to eliminate for traditional wastewater treatment processes; thus, they remain in the environment and may reenter our food chain (Juan Bofill 2023). Prevalence of MPs in the aquatic environment becomes a major concern. It has been reported that a majority of Indians, making up 50% and 80% of urban and rural populations, respectively, use untreated groundwater for their residential requirements (Chakraborti et al. 2010). In India, numerous research on the presence of different contaminants in surface water bodies, sludge, sediments, air, and soils have been conducted (Gani and Kazmi 2016). Besides pharmaceuticals, micropollutants also include substances that can disrupt the hormone level as well as endocrine-disrupting chemicals (EDCs), surfactants, phthalates, perfluoroalkyl substances (PFASs), household chemicals, perfumes, hormones, artificial sweeteners, and industrial chemical agents (Bradley et al. 2017). Several emerging pollutants have been detected in surface water, groundwater, drinking water, biosolid-amended soils (Chen et al. 2014), and sewage (Singh et al. 2021). In this context, they are best referred to as organic micropollutants (OMPs). It is important to note that OMPs can be found at trace concentrations, but some of these compounds pose a potential health and environmental risk as they tend to persist and bioaccumulate in the environment (Tiwari et al. 2017; Tousova et al. 2017). Therefore, biological potential treatment is the most costless method for removing OMPs and reducing their toxicity (Grandclément et al. 2017). Despite

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this, most wastewater treatment plants (WWTPs) do not achieve satisfactory removal (Falås et al. 2016). Explicit knowledge of OMP biotransformation mechanisms and limitations is key to minimizing their emissions into the environment. As suggested by Suárez et al. (2008) and Tiwari et al. (2017), operational parameters (temperature, pH, and time) are the main factors influencing biotransformation. Several attempts have been made to achieve 100% biotransformation efficiency by modified operational conditions and the microbiota of biological processes; although these strategies were sometimes successful, they often led to contradictory results. OMP biotransformation in various biological systems has been reported to be incomplete (Singhal and Perez-Garcia 2016). A steady concentration of OMPs occurs when biotransformation almost stops. In a batch experiment using activated sludge, both OMPs containing aliphatic amines and other OMPs with varying physicochemical properties were reported to have plateau values (Blair et al. 2015; Gulde et al. 2018). In addition to FernandezFontaina et al. (2014), fluoxetine biotransformation was observed to be quasiplateaus in simultaneous nitrifying reactors. In contrast, Xue et al. (2010) identified quasi-plateaus in anaerobic, anoxic, and anaerobic membrane bioreactors with aerobic biomass when fluoxetine was converted.

1.1

Current Status of Organic Micropollutants in the Environment

In recent years, OMPs have received increasing attention in ecosystem research. The health effects and ecotoxicological effects of these contaminants have been reported in various studies. In some cases, treating an overpolluted environment can be extremely expensive. There has been news that London’s drinking water contains synthetic estrogen due to excreted pill residues in the Thames River spread by six people (McKie 2012). Several First World countries have succeeded in reducing OMP concentrations in the surrounding by taking different appropriate regulatory measurements (Jones et al. 2005), which shifts the interest of researchers toward a novel type of organic-based pollutants (Saravanan et al. 2021). The levels of these contaminants in the wastewater discharge must be reduced to below 100 ng/L to minimize their negative health and ecotoxicological effects on human and also on animal health (Escher et al. 2011). For example, some critical reviews suggested that bisphenol A doses as low as four orders of magnitude below the currently prescribed level of 50 mg/kg/day effectively produced adverse effects in animals (Vandenberg et al. 2013). Moreover, the exposure of men to bisphenol A leads to changes in their sex hormones (Galloway et al. 2010). A wide range of OMP metabolites has been concluded in water bodies across the globe (Escher et al. 2014). Low concentrations of these substances are unlikely to cause acute toxicity, but long-term exposure may be harmful (Schriks et al. 2010). To detect the presence of micropollutants in groundwater, highly effective and widely utilized analytical analyses such as liquid

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chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) are used. As a result, several research organizations have researched and reported the existence of micropollutants from various regions of the world using these methodologies. Additionally, 4 out of 5 metabolites and 27 out of 32 pharmaceuticals were detected in European wastewater treatment plants where toxic effluents exceeded to one microgram per liter with maximum concentrations (Larsen et al. 2004), as well as active pharmaceutical ingredients, that include additives and different excipient formulations. Developing countries have been identified to have a high concentration of OMPs, and the majority of these contaminants are sold as over-the-counter in developing countries, resulting in higher concentrations in the surroundings (Stackelberg et al. 2004; García-Galán et al. 2010). Later, scientists tend to agree that classified management strategies need to develop and should be implemented (Brack et al. 2015) for a sustainable environment. For precise management with legislation regulating permissible level in the surrounding, it is necessary to understand both their fates in the environment and their harmful effects. As conventional sewage treatment plants are incapable of removing micropollutants and preventing the contamination of groundwater and soils, the Water Framework Directive (2000/60/ EC) (Lepper 2005) regulates a mission for the emission of some priority micropollutants. Through abiotic transformation, biodegradation, and/or sorption, micropollutants are removed from wastewater during the treatment process. A predominant role was reported to be played by the sorption of suspended solids to the surface and biodegradation. Even so, there is no general rule about how micropollutants are removed, since their relative contributions vary depending on their physicochemical properties, wastewater origin, composition, and operational parameters. Drugs and their metabolites are particularly important forms of OMPs because of their unknown effects and largely biological activities on the surrounding. A fullscale water treatment application using ozonation is extremely effective in reducing OMPs (von Gunten 2018). Through the production of free radicals from ozone decomposition, ozone reacts directly with organic compounds in water (von Gunten 2003). In terms of reaction kinetics, degradation, and identifying transformation products, the ozonation of single compound has been studied extensively (Ikehata et al. 2006). Advances in analytical techniques have made it possible to investigate the simultaneous ozonation process of mixture of OMPs. A wide range of compounds have been tested using multicomponent ozonation in labs, in pilot plants, and on a large scale (Kovalova et al. 2013). Despite this, some classes of OMPs, such as illicit drugs, remain less conclusively studied (Boleda et al. 2011). Organic compounds react with ozone in different ways such as the rate constants of their chemical structure are second-order and reach several orders of magnitude (Boleda et al. 2011). QSAR (quantitative structure-activity relationship) models can be used to estimate the kinetic parameters of ozonation reactions (Lee and Von Gunten 2012). The matrices of water, also recognized as surface water, have properties that correlate with dissolved ozone stability. The matrix components are also oxidant

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scavengers with increasing ozone doses required to reduce OMPs. In other words, ozonation can abate OMPs by altering kinetic and operational parameters (e.g., temperature, ozone dose) as well as the parameters of quality water (e.g., organic carbon concentration, alkalinity, pH) (Bourgin et al. 2017). In contrast, “according to the Planning Commission (2013),” there is no report to review the assessment of various contaminants present in the groundwater of different regions in India, where 80% of drinking water and 84% of irrigation are derived from groundwater (National Planning Commission 2013). As a result, it is crucial to compile the study conducted in India on the occurrence of micropollutants in groundwater. Also, the European Green Deal’s zero-pollution ambition to achieve a toxic-free environment protects both ecosystems and public health by avoiding harmful effects caused by chemical agents, including residues of certain pharmaceuticals in soil, air, and water. According to the newly adopted Farm to Fork Strategy by 2030, they aim to reduce the overall EU sales of antimicrobials for farmed animals and aquaculture by 50%, thus reducing the number of contaminants in the environment. Besides the eighth Environmental Action Programme (General Union Environment Action Programme 2021), the Circular Economy of Action Plan (Circular Economy Action Plan 2021), the Chemicals Strategy including Sustainability (Chemicals Strategy for Sustainability 2021), and Strategy of Biodiversity (EU Biodiversity Strategy 2021), many other initiatives serve as frameworks for shifting production and consumption toward a sustainable, safe, and environmentally benign method of generating and consuming resources, materials, and chemicals, taking the pollutants of emerging concern into account. Subsequently, in this chapter, we will discuss about several factors including origins, types, and its impacts on the human health and the environment, and we are also concerned about the lack of regulatory measures; continuous discharge of micropollutant may cause detrimental effect even though in its lower concentration.

2 Different Origins of Micropollutants A variety of transport and distribution routes can contribute to organic micropollutants reaching the environment. Chemicals’ physicochemical properties (e.g., water solubility, vapor pressure, and polarity) determine how they behave in the environment. In addition to atmospheric deposition, sewage treatment plant effluents and terrestrial runoff (from roofs, pavements, roads, and agricultural land) are major sources of emerging contaminants with environmental significance (Singh et al. 2021). Water pollution and intensive agriculture are major sources of OMPs that enter into the environment. After interacting with the environment, OMPs undergo various transformations including biochemical reactions, water dissolution, and insoluble solid matter (La Farre et al. 2008; Metcalfe et al. 2013). Approximately various OMPs are rapidly deteriorating, so the remainder is disseminated in the surrounding where the compound’s physicochemical properties

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determine its fate. These include stability, vapor pressure, water solubility including water splitting and the part of ecosystem to which these pollutants are disposed of, and also microbial metabolism (Daughton and Jones-Lepp 2001; Corcoran et al. 2010). In general, substances with low solubility in water are more toxic, persistent, and bioaccumulative than those with maximum solubility and may be examined at far-flung locations (La Farre et al. 2008). Comparatively, those pollutants having maximum dissolution and maximum degree of conversion are furthermore broadly dispensed in a brief period compared to compounds with lower solubility (Boxall et al. 2012). After that, metabolic ventures can then convert them into compounds with more availability than before via several routes depending on the metabolic process (Boxall et al. 2012; Zhang et al. 2008). Since most of these compounds cannot be metabolized completely within animals, the parent molecules are excreted into the surrounding along with the metabolites (Carballa et al. 2004). Most antibiotics are excreted without molecular modification (Sarmah et al. 2006; Kümmerer 2009). Several OMPs are ignored during secondary and tertiary treatment in wastewater treatment plants (Castiglioni et al. 2006), while others enter freshwater resources and become involved in food cycles. In a number of cases, OMPs are drugs used for animals or humans, antibiotics, a range of toiletries, personal hygiene products, cosmetics, etc. These are basically organic compounds synthesized to control the metabolic processes that occur in human and animal bodies. Many types of pesticides remain in the surrounding; only a minimal percentage are degraded through different physical and biological methods, with the other attaching themselves to thin particles of soil and organic materials, evaporating into the air, and/or leaching into groundwater. A variety of residues are carried by surface water into drinking water resources, including rivers, lakes, and canals, by runoff water from agricultural lands. Several OMPs are also produced by cosmetics, personal care products (PCPs), pharmaceuticals, pesticides, herbicides, fertilizers, perfluoroalkyl substances (PFAS), artificial sweeteners, phthalates, estrogens, hormones, and industrial chemicals. Different sources of OMPs are classified in three broad categories as shown in Fig. 1. In general, the fate of chemicals is influenced by their adsorption ability according to their hydrophobicity and/or electrostaticity (Fent et al. 2006). Due to the chemicals’ kinetic inertness, they are typically ejected through the body in several unmodified conjugates. As a result, the substituents set off constituents of wastewater and they may play out into canals, rivers, and irrigation water including treatment plants, depending on their chemical composition. Upon ingestion and subsequent excretion, pharmaceuticals enter aquatic systems in the form of their non-metabolized parent compounds or metabolites. In comparison to basic pharmaceuticals, acidic pharmaceuticals (which are ionic at neutral pH) show minimal adsorption prospects to different wastewater sludges. An additional class of OMPs comprises toxic chemical agents used for sanitation purposes. For instance, waterborne pathogens and diseases are controlled by disinfecting swimming pools. Different disinfection agents like chlorine dioxide, chlorine, and ozone including chloramine react with different organic matters to produce different disinfection by-products (DBPs).

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Fig. 1 Major sources/origins of a wide range of micropollutants present in the environment

In general, haloacetic acids and trihalomethanes (THMs) predominate in the composition of DBP loads; the eventual fates of contaminants depend on its treatment system and nature before it enters the water bodies. A group of OMPs also includes chemicals designed for industrial uses, for example, carpeting, upholstery, clothing, food paper wrappers, metal plating, and firefighting foams. Some of these chemicals have already been designated as priority micropollutants, for example, chlorinated solvents, adipates, phthalates, methyl tert-butyl ether, and fuel oxygenates; as a result of the transformation, some contaminants are converted into higher toxic metabolites, including 1,4-dioxane, benzotriazole intermediates, perfluorinated compounds (PFCs), and various dioxins. It is not only the ecotoxicity of OMPs that causes genotoxicity; they may also cause point mutations, chromosome rearrangements, deletions, inversions, insertions, or persisting epigenetic modifications such as methylation of deoxyribonucleotides (DNA) and phosphorylation of

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histones. Moreover, genotoxicity can affect germinal and somatic cells, causing harmful effects within a single generation or across generations. A presence of long-term different vital metabolites may also alter epigenetic pathways. As an example, minimal concentrations of different hydralazines, and an antihypertensive, inhibit DNA methylation, leading to uncontrolled expression of gene. Ultimately, the contaminant’s toxicity and the length of exposure are responsible for these genetic changes. Several OMPs are especially bioactively designed at very little concentrations, so their presence in the environment at such little concentrations may harm living organisms. It is estimated that humans spend 90% of their time indoors. Some environmental contaminants are found in the indoor environment, which is emerging as a health concern. Household products and building materials contribute to a significant proportion of OMPs in indoor dust. Aside from that, they might also arise from outdoor environments. House dust contains chemical compounds that can be ingested through hand-to-mouth contact, absorbed through the skin, or inhaled via resuspended dust. In addition to harmful effects on microorganisms and plants, OMPs may also adversely affect animals directly or indirectly, especially by feeding macroinvertebrates in the food chain. There has been evidence that polybrominated diphenyl ether (PBDE) flame retardants have now been biomagnified significantly in suckers and osprey eggs, even though their concentration does not seem to be predominant in the biomass of invertebrates. In the next section, a brief insight on the different types of micropollutants present in the environmental components has been given.

3 Types of Micropollutants Micropollutants are microlevel pollutants comprising different materials which may contain different substances, such as flame retardants, pharmaceuticals, perfumes, waterproofing agents, pesticides, cosmetics, foam insulators, and plasticizers. Some of the endocrine-disrupting compounds (EDC) comprise endogenously created hormones, mycoestrogens—fungi-originated organic compounds—micropollutants, surfactants, polycyclic aromatic hydrocarbons (PAHs), pesticides, different types of halo-organic compounds including dioxins and furans, and types of steroid estrogens (SEs), for example, estrone (E1), estradiol (E2), and ethinylestradiol (EE2) (Lloret et al. 2012). Micropollutants constitute biological or chemical contaminants which make passes into ground and surface waters in trace quantities. Micropollutants are frequently discharged to surface waters without being further treated the wastewater produced from various treatment plants. Micropollutants are found to be present in surface water which is frequently supplied to wastewater treatment plants (WWTP). It has been estimated that the chemical products hold a global share of worth $5000B (Asthana 2014). Recently, there is substantial rise in awareness in the European

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Union (EU) on issues related to the quality of water since the WWTPs contribute primarily to MP pollution (Corominas et al. 2013). Micropollutants consist of natural and anthropogenic substances, including pharmaceuticals, antibiotics, and personal care and industrial chemicals. Endocrine-disrupting chemicals (EDC), for example, insecticides, bisphenol A, natural hormones, nonylphenol, and perfluorooctanesulfonic acid (PFOS), are a few major MPs. MPs are called so because they are synthetically produced, nonnatural micropollutants, which are found in the smallest concentrations of billionths to millionths of a gram per liter. Till date, most of the researchers have recognized that in water bodies, WWTPs are being the primary cause of MPs. MPs that are accumulated in soil are released into aquatic bodies through leaching or runoff process which is harmful to the aquatic organisms thereof. The different kinds of micropollutants are presented as follows:

3.1

Pharmaceuticals

Many pharmaceutical products are used by several people worldwide. Pharmaceutical products are most often detected in various sources of aquatic environments, originating from convenience stores, drugs stores, and hospitals. Some of the pharmaceutical’s by-products like ibuprofen or paracetamol can successfully be eliminated by traditional treatment process (Ratola et al. 2012). Besides, a report on removal of 13% and 17–23% chemicals like sulfamethazine or carbamazepine, respectively, from wastewater was presented (Ratola et al. 2012). Although the body does absorb some of the chemicals contained with them, many pass through the digestive system and are secreted by urine. Pharmaceutical compounds can be metabolized inside the organisms either completely or partially, some parts are unchanged parent drugs, and via urine and/or feces, the produced metabolite excretion is done (Ribeiro et al. 2016). Even though a number of compounds are found to be present in the effluents produced from treatment methods, antibiotics are the major class of such compounds that attracts the attention of the environmentalists and researchers. Assessing the toxic impact associated with pharmaceuticals and their by-products or their mixtures is imposing a real challenge for the researchers and scientists.

3.2

Heavy Metals

Several heavy metals are an inevitable part of the earth’s crust and the environment. Metals such as Fe and Zn belong to essential nutrients required for proper functioning and growth of our body. However, extraction and application processes of heavy metals in numerous products can lead to leaching into the environment. Metals such as Ag, Zn, Fe, Ni, Cu, etc. are found in nanotraces in wastewaters. Other than these

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Fig. 2 Nanomaterials as a potential sources of micropollution

Commercially available Nps

Graphene based nanoparcle

Metal oxide Nps and composies

metals, some metals exist in the form of a nanoscale such as metal oxides of Ti, Fe, Si, Ce, and Al (viz., TiO2, Fe3O4, SiO2, CeO2, and Al2O3, respectively) and carbonbased NPs in the form of graphene, fullerene, and/or nanotubes, as well as nonmetals, particularly Si and quantum dots (Madeła et al. 2016) as shown in Fig. 2.

3.3

Cosmetics and Personal Care Products

Many household items which are in our day-to-day use such as shampoos, skin creams, and toothpastes contain a cocktail of chemicals, hormones, and other persistent elements which do not disappear once they have been washed off our bodies (Madeła et al. 2016). Similarly, other types of products such as paints, varnishes, flame retardants, ultraviolet protection substances, and packaging materials can contain micropollutants. Other products like detergents, antifreezers, and corrosion protectors contain MPs of concentration as high as 22.1 μg/L–24.3 μg/L (Deeb et al. 2017). In addition, there are a number of micropollutants present in the environment. A detailed insight on the types of different micropollutants have been given on the introductory chapters of the book.

4 Occurrence of Micropollutants The discharge of WWTP effluent is the major contributor in emerging micropollutants (EMPs), which run offs to water bodies and can have short- as well as long-term toxic effects on marine ecosystem which results in endocrine disruption and increased antibiotic resistance in marine animals (Fent et al. 2006; Pruden et al. 2006; Kasprzyk-Hordern et al. 2009). The presence of micropollutants in surface water has been widely reported. Wastewater tanks (WWTs) can release

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wastewater effluents containing high concentration of MPs directly in water bodies: rivers, lakes, oceans, and reservoirs. Further, these MPs either get deposited on sediments or transferred to other regions under hydrological effect. Simultaneously, these compounds can undergo chemical and biological degradation to form other harmful by-products. Among different OMPs, this chapter highlights the occurrence of pesticides and pharmaceutical residues present in the environment as follows:

4.1

Pesticides

Pesticides are mixtures of chemical substances which increase the agricultural productivity by protecting the plants. Although pesticides play a key role in elevating the modern agricultural productions both qualitatively and quantitatively, exposure to them over a long period will have severe adversities on human and animal health (Dasgupta et al. 2007). A significant part of these negative effects is due to the dispensing of doses of these pesticides to agricultural areas in an inappropriate way (Dasgupta et al. 2007; Cancino et al. 2023; Shahid et al. 2023).

4.2

Pharmaceutical Residues

A plethora of articles reports the occurrence of pharmaceutical residues and various kinds of hormones in surface water and sewage water (Thomas 1998). With the rising global population, a proportional increase in the application of medicines consequently increases the presence of such hazardous chemicals in the environment (Wooten 2012). As a result, WWTPs will produce effluents heavily loaded with pharmaceutical residues up to the micropollutant level. The conventional sewage treatment plants are also no less in producing effluents with high concentration of drug substances, which is also persistent in surface waters as well as increasing their high biological stability (Brillas et al. 2010).

5 Adverse Impacts of Micropollutants on Human Health Despite low yield and concentrations, the effects of a special class of MPs leads to severe hazards to the life on earth as well as underwater. Other MPs like polyfluoroalkyl can undergo biomagnification inside the body in the long run that can actually cause serious health issues, for example, weakening of the immune system leading to disruptions of thyroid hormone and ultimately to cancer (Lee 2018). Surface water remains a major source of potable water in most part of the world. Thus, MPs present in surface water, in WWTPs, and in drinking water are

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reported to have high concentration of MPs (>165 ng/L). In other words, WWTPs are not capable enough of completing the removal of these micro-contaminants. A holistic approach should be adopted to eliminate the MPs from drinking water taking different characteristics and behaviors of MPs into consideration. However, only a few numbers of developed countries like Switzerland are practicing the complete removal of these MPs using modern techniques and processes in anticipation of regulating norms of safe drinking water in the entire European Union (EU). Several EU Member States are considering addition of more treatment steps for the reduction of micropollutants in treated wastewater.

6 Micropollutants and Their Impacts on the Environment Micropollutants are contaminants that are widespread in our environment and ecosystem. They exist in the environment at trace concentrations from micrograms to kilograms. They can be found in personal care and pharmaceutical products, polyfluoroalkyl and polycyclic aromatic hydrocarbon substances, nanomaterials, pesticides, steroids, and plasticizers. Potential levels of metals present in the environment and beyond will create disturbances in the ecosystem of living organisms. The rise in contaminants which is often left unmonitored potentially threatens the human life and environment. Micropollutants have become an alarm for the entire population owing to their dangers to health and ecosystem (Lin et al. 2016). Produced by various sources, micropollutants are now found in food and drinking water. As mentioned in the US Geological Survey, micropollutants are characterized as “any compound of engineered root or any microorganism that is not usually observed in the surrounding, however it can possibly cause unfriendly environmental and additionally human wellbeing impacts” (Sivaranjanee and Kumar 2021). In another study, Dulio et al. (2018) have reported micropollutants as those substances that can continue to exist anywhere in the ecosystem, which are essentially lifethreatening and causing health problems, e.g., neurodevelopmental delays, thus possibly affecting the human immune system. It is important to note that most contaminants are not new to the ecosystem. Hence, these components are commonly named as “chemicals of emerging concern” or “contaminants of emerging concern” (Sivaranjanee and Kumar 2021). Urbanization and the rapidly growing population have impacted the quality of resources due to contamination. Heavy metals and microbial pollutants are the frequently investigated topics to evaluate the water quality. Studies reveal that the existence of these pollutants has a great impact on water components. The problem is due to the unawareness about the long-term effects of these pollutants on marine and terrestrial life, health, environment, etc. The discovery of toxic materials in the water surface is of public concern (Khatib et al. 2019). Reports were found on the assessment of the MP sources that contaminates the water bodies (Lim et al. 2017). Due to the lack of proper and organized monitoring systems, the condition of drinking water treatment is still constrained. However, policy makers of various

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governments have addressed the concern by setting regulatory frameworks involving commercialization and other emissions in the environment. The following are the possible micropollutants that are distributed into the atmosphere and dissolve into various living species. Few studies have considered using pharmaceuticals as a significant factor contributing toward pollution in the environment. It includes waste discharge from hospitals and other treatment processes (Lim et al. 2017). Antibiotics are also considered as emerging water pollutants that focus on the technologies addressing treatment like photocatalytic deprivation that challenges health (Reemtsma et al. 2013). Medications and other personal care products also include chemicals that are significant sources of micropollutants. After being released from farmland manure, these pollutants mix in the community (ParraSaldivar et al. 2020). In this process, there is a widespread presence of compounds that are hazardous. On the other hand, antiseptics are easily available and are consumable for household purposes. This in turn can deform in the environment that possesses highest concentrations and has been noticed in numerous water bodies that raises the question of safety standards of triclosan in water that is used for drinking purposes. Over-the-counter drugs contain steroid hormones that are used extensively in humans and animals but eventually trigger the functions in the body and overall health system. Additionally, perfluorinated compounds are applied in food packaging, adhesives, and repellents, among other things, where perfluorooctanoic acid is the most used and is noticed in drinking water sources which is harmful for the human health (Lee 2018). Pesticides, on the other hand, can contaminate drinking water due to lack of caution. Insecticide metabolites are extremely exposed to leaching soil with the diversity being assigned to multiple pesticide applications in metropolitan areas and agricultural activities and thereby micropollutant concentrations in several water bodies across the globe (Reemtsma et al. 2013). Micropollutants have harmful effects and have drawn a major concern since they can cause cancer and other health issues. They can hinder hormone production and distress the living organisms on earth. Some of the problems include disruption of hormone levels, hormone production, and metabolism and many more effects (Lee 2018). When a vulnerable individual is exposed to micropollutants, sex hormones are affected, thereby impacting the sexual development of the individual (Nesan et al. 2018). Hormones, such as norethindrone, mestranol, and equilenin, are regarded as primary MPs of drinking water contaminants because of their health hazards and ecological incidence (Richardson and Kimura 2020). Using triclocarban-containing personal care and hygiene products can cause hormonal dysfunctions. Similarly, skincare constituents also contain triclocarban that may disrupt body’s hormonal conditions (Li et al. 2018). Triclosan, as per Fu et al. (2020), can disturb the reproductive alignment and cause thyroid issues. A comprehensive study revealed that exposure to bisphenol A (BPA) can affect both human and animal health, e.g., affecting sperm quality and causing fertility and sex-related hormonal issues in males (Rochester and Bisphenol 2013; Weber et al. 2015). On the other hand, it has more adverse effects in women like breast cancer, polycystic ovary

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syndrome, miscarriages, and premature births. Congenital disabilities and cancer are correlated with consumption of drinking water contaminated with disinfection by-products (DBPs). In addition, DBPs present in pool water can also cause health problems among individuals. The risk of cancer is associated with exposure to trihalomethanes as mentioned by Gan et al. (2013). Moreover, pesticide components can interrupt activities in the endocrine system (Mostafalou and Abdollahi 2013). Also, organochlorine accumulation is related to a greater risk of genotoxicity and other psychomotor development (Souza et al. 2020). Elimination of micropollutants from the water will determine the water quality of drinking water. This may be eliminated by adopting biological and oxidation systems. Moreover, in certain cases, treatment processes are difficult to optimize because of their high maintenance cost along with their complicated procedures. During the 1900s, microbial biomass has been utilized for cutting down nutrients and other contaminants in wastewater. In contrast, the usage of similar biological treatment is not common in drinking water solutions. Nonetheless, science and advancements have started to develop the possibility of technologies in drinking water. Physicochemical procedures are performed to reduce turbidity that eventually minimizes the concentration of MPs in water. (Benner et al. 2013). Factors like activated carbon are part of the physicochemical process. Additionally, oxidation is considered fundamental for removing micropollutants. Therefore, the choice of oxidant is very important and ozone (O3), being highly oxidant, has broadly been used in water disinfection treatments. O3 treatment involves reaction of organic MPs directly with molecular O3 or indirectly with O3• during decomposition (Saravanan et al. 2021). The consequence caused by micropollutants to the ecosystem and human health is inevitable. It has tremendous impacts globally. In the rapid development of micropollutants, the greatest challenge for policy makers is to frame guidelines for assessing the risk and hazards related to MPs. However, it is a task in water management to make it sustainable and population growth further worsens sources of water and its treatment. Because MPs are small in size, they are difficult to remove by common water treatment processes from the water where they are dissolved. Thus, WWTPs are crucial in eliminating them before they get discharged into the water bodies. In many cases, some of the MPs are found to be present even after the treatment. Moreover, the chemical scum gets mixed with the atmospheric gases which are then washed down by rain and pollute the surface water. The list of contaminants including environmental impact might be recorded in the different form of a literature catalogue. It may contain information regarding metabolite interactions and fate in ecosystems. To deal with and plan for the probable coercions, it may be helpful to have information about persistence, toxicity at individual and also complex levels, and leachability. To assess and address the potential risks of OMPs on a scientific, managerial, and ethical basis, working groups may be formed between intergovernmental and nongovernmental organizations. Several micropollutants reported in the Indian groundwater include pharmaceuticals, PCPs (personal care products), ASW (artificial sweetener), pesticides,

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phthalate surfactants, PFAS (per- and poly-fluoroalkyl substances), and EDC (endocrine-disrupting compounds). For the removal of OMPs from the environment, nonbiological remediation methods may be useful. Physicochemical methods such as membrane ultrafiltration, advanced oxidation, activated carbon adsorption, hydrostatic exclusion, and electrostatic exclusion are used significantly. Furthermore, OMPs can be bioremediated into benign products by modifying conventional bioremediation procedures. There are several methods for reducing lignin emissions, including different ligninolytic enzymes (e.g., laccase), biological trickling filter beds, and membrane biological reactors including constructed wetlands, with plant-bacteria partnerships. In some instances, combining non-biological and biological methods can be beneficial for maximizing removal efficiency. A majority of studies in India focused on pesticides and pharmaceuticals as micropollutants. There have been very few surveys on emerging micropollutants in the groundwater of India compared with other countries. Various studies of micropollutants, for example, food additives and other flame retardants, have yet to be conducted. Some of the challenges faced include lack of sophisticated facilities and reliable procedures and high costs. Only a small percentage of the Indian geographical area has been explored in the few studies conducted. Therefore, more regions need to be included in micropollutant studies. Hence, research initiatives are needed in the future that will emphasize the impacts of pollutants on human health allowing for integrated research to improve the environmental situation at a large scale.

7 Conclusions and Future Prospects Many developed countries have now acknowledged that their environments are contaminated by OMPs. Despite their ubiquitous presence, these chemicals are almost invisible due to minimal concentrations in the environment. The present chapter highlights the sources and impacts of various micropollutants on the environment and human health. To deal with future concerns related to the OMPs, guidelines and values for water and regulations for all micropollutants should be developed. Furthermore, we believe that environmental integrity and ecological safety authorities worldwide must become proactive to avoid severe environmental damage caused by OMPs. To detect and analyze OMPs and their metabolites, we need (i) different vigorous and cost-effective pathways for the determination and analysis, (ii) a comprehensive study of toxicological significance of MPs on the system, and (iii) development of novel cost-effective technologies for mitigation of MPs (Sarma et al. 2022). Before assessing risks and managing hazards, we need to assess different environmental effects of micropollutants. A huge step forward would be to find environmentally friendly alternatives to most harmful OMPs. For the evaluation of biologically active OMPs, effective risk assessment approaches must also be considered. Some of the potential approaches for preventing OMP inputs in the environment in the future are the following:

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1. Advanced Water Treatment Technologies: Development of water treatment technologies helps in removing OMPs efficiently from the water sources, which includes the use of some advanced oxidation processes (AOPs) such as ozonation, photocatalysis, and different electrochemical oxidation, which can effectively reduce organic pollutants. 2. Membrane Technologies: Various advancements in membrane filtration technologies can inflate the removal of OMPs from water. Reverse osmosis membranes and nanofiltration can effectively separate and remove micropollutants, which include organic compounds, from different water sources. 3. Improved Monitoring and Detection Systems: Development of advanced monitoring and several detection systems can aid in identifying and quantifying some OMPs in water bodies. These systems also include some real-time sensors, remote sensing technologies, and other analytical techniques which can provide an accurate and rapid detection of OMPs. 4. Green Chemistry and Sustainable Manufacturing: Green chemistry principles and several sustainable manufacturing practices can be enhanced to reduce the discharge of OMPs in water bodies. These involve designing and manufacturing chemicals and products that are not harmful to the environment and using cleaner production techniques. 5. Public Awareness and Education: In order to promote responsible consumption and disposal of OMPs, the public needs to become more aware of the environmental impacts of micropollutants. It is important to educate individuals about the proper use and disposal of pharmaceuticals, personal care products, and other potential sources of micropollutants. 6. Regulatory Measures: It is possible to significantly reduce OMPs’ presence in the environment by strengthening and implementing regulatory measures to control their use and discharge. Chemicals used in consumer products can also be subjected to stricter regulations, such as those on industrial discharges and wastewater treatment standards. 7. Research and Development: In order to develop innovative solutions for inhibiting OMPs, research and development efforts will need to continue to understand how OMPs behave and what they can do in different environments. Developing effective treatment methods for emerging contaminants requires studying and evaluating their potential risks. It is important to note that inhibiting OMPs requires a combination of technological, societal, and regulatory efforts. To resolve this environmental challenge in a sustainable and long-term manner, researchers, policymakers, and industries must collaborate.

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Contamination of Aquatic Ecosystem with Pharmaceutical and Personal Care Micropollutants Siddhant Srivastava and Swati Sachdev

Abstract The event of micropollutant occurrence in the water ecosystem from the past few decades has become a matter of solicitude. Micropollutants are the emerging contaminants that include an array of anthropogenic and natural substances, particularly pharmaceutical products like antibiotics and personal care products. Studies suggest that consumption of products containing pharmaceutical compounds is metabolized in the body and is eventually released into water bodies via urine and feces. The presence of micropollutants in the water bodies is linked with an array of short- and long-term toxicity in living beings and antibiotic resistance in pathogenic microorganisms. The wastewater treatment plant (WWTP) practices adopted are not particularly tailored to remove micropollutants of pharmaceuticals and personal care products (PPCPs). Thus, several micropollutants pass through the treatment process. Moreover, owing to persisting nature and continuous introduction, they are often detected in aquatic environment. Presently, the guidelines and standards regarding discharge of most of the micropollutants do not exist. Moreover, comprehensive scenarios on existence of various micropollutants in water bodies and their elimination via existing treatment processes are not well documented. The present chapter attempts to furnish details on the contamination of aquatic ecosystems with PPCP micropollutants, discusses their impact on humans and the environment, and delineates the role of bioremediation in their management. Keywords Antibiotic resistance · Bioremediation · Emerging contaminants · Endocrine disruptors · Wastewater treatment plant

S. Srivastava Department of Pharmacy, Lucknow Model College of Pharmacy, Saudruana, Lucknow, Uttar Pradesh, India Department of Pharmaceutics, IPSR Group of Institutions, Sohramau, Unnao, Uttar Pradesh, India S. Sachdev (✉) Department of Liberal Education, Era University, Sarfarazganj, Lucknow, Uttar Pradesh, India e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 R. Bhadouria et al. (eds.), Organic Micropollutants in Aquatic and Terrestrial Environments, https://doi.org/10.1007/978-3-031-48977-8_2

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1 Introduction The exponential rise in human population and increased industrialization have resulted in the contamination of the environment with micropollutants. Micropollutants are the emerging pollutants (Arman et al. 2021), whose escalated release in aquatic ecosystems has levied adverse influence on humans and ecosystem balance (Palma et al. 2020). Organic micropollutants include pharmaceutical products like antibiotics, hormones, lipid regulators, antidepressants, nonsteroidal antiinflammatory drugs, and antihypertensives (Cizmas et al. 2015), pesticides, and personal care products (PCPs), which are used extensively in healthcare, agriculture, and self-care sectors and have emerged as significant contaminants of the aquatic ecosystem (Arman et al. 2021). These pollutants and their metabolites either are discharged directly into the water ecosystem through sewage disposal and agricultural runoff or are leached from contaminated soil (Arman et al. 2021). Studies have well-established the presence of micropollutants in municipal wastewater, fresh water bodies, and potable water (Arman et al. 2021). Nearly 700 different types of emerging pollutants and their biotransformation products have been reported in the European aquatic environment (Dulio et al. 2018). The occurrence of micropollutants in several surface waters around the world has posed great environmental challenges in recent years. Emerging pollutants are found in the environment in trace amounts and exhibit the property to persist in the environment, bioaccumulate in living tissues, and can be a probable menace to the biotic components of the environment resulting in abnormal growth, neurodevelopmental delay, abridge fertility and reproductive health, affect wildlife, and harm the immune system in humans (Arman et al. 2021). Such pollutants are not new which have been introduced lately into the environment, but the toxic impact of these pollutants has been discovered in the near past (Arman et al. 2021). The emerging pollutants have not been earlier monitored constantly in the environment due to their presence in minute quantity and lack of strict regulatory norms for micropollutants, but now are being seriously examined as they have been reported to influence the functions of the aquatic ecosystem (Bolong et al. 2009; Geissen et al. 2015). Among various organic micropollutants, pharmaceutical and personal care products (PPCPs), which are developing micropollutants, are frequently found in water bodies due to their comprehensive use for treating diseases in humans and animals and personal hygiene, grooming, cleaning, and beautification (Kookana et al. 2014; Khalid and Abdollahi 2021; Priya et al. 2022). PPCPs such as antibiotics, analgesics, steroids, antidepressants, fragrances, cosmetics, and other compounds are used regularly (Sui et al. 2015). PPCPs are also referred to as “pseudo”-persistent organic compounds due to their physicochemical characteristics and concentration present in the environment (Chakraborty et al. 2019). These organic micropollutants have gained scientific and public attention worldwide due to their persistent nature and toxicity-causing potential (Li et al. 2019). PPCPs can induce metabolic effects on human beings even at trace concentrations (Krishnan et al. 2021), affect other living organisms, and can disrupt ecological balance (Chakraborty et al. 2019). Active

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pharmaceutical ingredients (API) in pharmaceutical products used to cure illness are biologically active compounds at low concentration and their unintended presence in the environment exhibits deleterious impression on nontarget biota (Kookana et al. 2014). For example, the residue of diclofenac in the tissues of cattle on consumption by vultures resulted in renal failure and visceral gout, which eventually caused the extensive decline in the population of some species of vulture in Asia (Oaks et al. 2004). The PPCPs can plunge into the environment in all phases of life cycle, i.e., production, consumption, and disposal. For instance, only a small fraction of pharmaceutical products consumed by humans are metabolized in the body, while most of it, sometimes 90%, remain as such and are excreted out and end up into the wastewater (Krishnan et al. 2021). The wastewater-containing PPCPs, even after treatment in a wastewater treatment plant (WWTP), retain micropollutants, due to incompetence of existing treatment facilities to obliterate such contaminants; hence, they manage to reach water bodies and consequently to potable water (Kumar et al. 2019; Krishnan et al. 2021; Priya et al. 2022). Moreover, utilization of contaminated water for irrigation causes the uptake of PPCP residues by plants. Presence of PPCP micropollutants in plants and aquatic animals eventually introduces them to the food chain, increasing health hazards in human beings (Narayanan et al. 2022). These micropollutants have received scientific and public attention at the global level due to their ability to induce resistance in microorganisms and affect the endocrine system (Bolong et al. 2009; Priya et al. 2022). The behavior and the induced health hazard of these organic micropollutants are not well-understood. Moreover, only marginal researches have been undertaken to assess the contamination level and toxicity of PPCPs. Hence, the purpose of this chapter is to spotlight the concern pertaining to environmental and health hazards linked with the contamination of aquatic ecosystems with PPCP micropollutants, to enhance the understanding of the origin, fate, and effects of micropollutants on living organisms. Further, this chapter chalk out the methods that can effectively eliminate emerging pollutants from the environment.

2 Sources of PPCPs in Aquatic Ecosystem and Food Chain PPCPs are utilized in everyday activity and are released into our environment. Pharmaceuticals are important constituents of medical practice used in multiple spheres from diagnosis to treatment/disease prevention, whereas personal care products like soap, detergent, sanitizer, baby care products, mosquito repellents, sunscreen lotion, and fragrances are used in a routine to promote personal hygiene and enhance beauty (Chakraborty et al. 2019; Khalid and Abdollahi 2021). The most crucial sources of PPCPs in water bodies include effluent from WWTPs that receive human waste, waste from hospitals, and industries, agricultural fields (particularly involved in intensive livestock farming), and waste management facilities (landfills) (Sui et al. 2015; Krishnan et al. 2021; Singh et al. 2021a; Adeleye et al. 2022). Direct

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Manufacturing industries Landfills

Personal health care & hygiene PPCPs

Hospitals and Clinics

Wastewater treatment plant

Aquatic ecosystem

Aquaculture

Soil Agriculture & Animal husbandry Application of PPCPs

Disposal in Environment

Ultimate fate

Fig. 1 Direct and indirect sources of PPCPs in aquatic ecosystem. Production and consumption of PPCPs; both are responsible for PPCP contamination in aquatic ecosystem along with incompetent wastewater treatment, application of PPCPs containing waste (sludge) on soil, and improper dumping of waste in landfills

and indirect sources resulting in contamination of aquatic environment with PPCPs are presented in Fig. 1.

2.1

Wastewater Treatment Plant: A Potential Source of PPCPs in Aquatic Ecosystem

Wastewater treatment plants (WWTPs) are considered as a major source of PPCP pollution in aquatic ecosystems (Sui et al. 2015), which receive influent from domestic, agricultural, industrial, and hospital settings containing recalcitrant and/or partially degraded PPCPs (Meyer et al. 2019; Krishnan et al. 2021). A work is undertaken to assess the presence of 37 pharmaceutical compounds along with endocrine disruptors in the samples of WWTP wastewater, along with raw potable water in Lausanne, Switzerland (Morasch et al. 2010). The observed results confirmed that all pharmaceutical and other micropollutants except 17-ɑ-ethinylestradiol were present in WWTP wastewater. Analogously, 22 pharmaceuticals including paracetamol, ciprofloxacin, and sulfamethoxazole were reported in raw potable water in a concentration above the predicted no-effect concentration.

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This shows that the level of contamination of raw drinking water with these pharmaceuticals can be a threat to an ecosystem.

2.2

Regular Consumption of PPCPs

The consumption of PPCPs is the most important aspect that promotes the release of PPCPs in waterways via WWTP. Most of the global population has been discovered to consume milligrams to grams of drugs in day-to-day life (Narayanan et al. 2022). In Asia and India, 65,400 and 1500 tons of acetaminophen are consumed per month, respectively (Kumar et al. 2019). In terms of pharmaceutical product production, India stands at the third position in the world and holds 13th rank in consumption (Kumar et al. 2019). The consumption of antimicrobials at the global level has been anticipated to increase by 67%, between 2010 and 2030 (Kumar et al. 2019). In India alone, the consumption of antibiotics has increased from 3.2 to 6.5 billion tons from 2010 to 2015 (Kumar et al. 2019; Singh et al. 2021b). This shows that consumption of pharmaceuticals has been elevated, probably owing to improved accessibility to healthcare services and better disease diagnosis. Besides, PCP use frequency depends on the availability of the products and socioeconomic status as well as lifestyle of an individual (Khalid and Abdollahi 2021). After consumption, the parent compounds of PPCPs and their metabolites are excreted out and enter the sewage system (Sui et al. 2015). In addition to human medicines, pharmaceutical products are used to cure diseases in animals and are often released directly to the water bodies via application in aquaculture and animal husbandry, and/or indirectly released on use of contaminated livestock manure on agricultural soil as fertilizer (Boxall et al. 2012). PPCPs eventually are moved to the surface waters through the direct release of wastewater effluent, leaks in WWTP, and/or surface runoff (Kinney et al. 2006; Meyer et al. 2019; Krishnan et al. 2021). The PPCPs present in surface water can be transferred gradually to the groundwater via vertical or lateral hydraulic exchange (Sui et al. 2015). PPCPs, upon reaching the aquatic ecosystems, are either degraded, adsorbed to organic matter, bioaccumulated in tissues, and biomagnified with the food chain and/or metabolized by the organisms (Meyer et al. 2019). PPCPs like nonsteroidal anti-inflammatory drugs (NSAIDs) like diclofenac and ibuprofen, UV light-absorbing compounds like oxybenzone which are used in sunscreen and plastics, methylparaben that is used in pharmaceutical and cosmetics as preservative, carbamazepine (an antiepileptic drug), nonylphenol polyethoxylate (nonionic surfactant), warfarin (anticoagulant), diphenhydramine (antihistamine), venlafaxine (antidepressant), and many others have been found in sludge, sewage, and/or water (Narayanan et al. 2022). The actual amount of PPCPs that enter the aquatic ecosystem is not well characterized, but several studies have proven the widespread occurrence of these micropollutants (Cizmas et al. 2015). Show et al. (2021) reported detectable levels of carbamazepine (1.5%), caffeine (0.24%), acetaminophen (0.32%), and sulfamethoxazole (0.41%) in drinking as well as in surface water. Analogously, Wang et al. (2015) assessed urban

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river water samples collected from major cities of China, i.e., Beijing, Changzhou, and Shenzhen, for the presence of 36 PPCPs and found 28 compounds in the samples. Among these contaminants, half of the compounds were antibiotics. Further, WWTPs were reported to be major PPCP contamination sources for the investigated aquatic sites. Several researchers have detected various PPCPs in the aquatic environment in different parts of the world (Moldovan 2006; Qiao et al. 2011; Oliveira et al. 2015), which delineates the fact that PPCP contamination in water is ubiquitous and needs to be addressed immediately to alleviate the associated health risk.

2.3

Landfill Leachates

Another important source of PPCP in aquatic ecosystems is leachate that originated from landfills (Krishnan et al. 2021). PPCP-contaminated waste dumped in landfills or animal waste applied on soil as fertilizers result in the leaching of micropollutants, which ultimately move to the groundwater (Krishnan et al. 2021). Improper disposal of unused or expired PPCPs is also a source of contamination of water resources with organic micropollutants (Krishnan et al. 2021). Expired or unused products are often discarded by dumping in landfills or in lavatories, from where these micropollutants find their way to the aquatic environment. Moreover, PCPs applied over the skin or external body surfaces such as moisturizers, sunscreen, and others are washed off and released in water via routine activities like bathing and swimming (Krishnan et al. 2021; Slosarczyk et al. 2021). The occurrence of PPCPs in an aquatic ecosystem is a significant cause of concern as these pollutants are polar and hydrophilic and show low volatility, which enhances their transportation range and incorporation in the food chain (Krishnan et al. 2021) that increase the risk of toxicity in living beings. Thus, it is crucial to establish different routes of introduction of PPCPs into the aquatic ecosystem to minimize pollution and alleviate ecological risk.

3 Environmental and Biological Effects of PPCPs The presence of PPCP micropollutants in water ecosystems is a potential hazard for aquatic life and human beings (Fig. 2). PPCPs are persistent compounds that show recalcitrant attributes toward microbial degradation and bear synergistic effects with other pollutants (Onesios et al. 2009). PPCPs as well as their metabolites can react with specific contaminants via precipitation reaction and generate more complex forms of pollutants that exhibit higher toxicity and have the ability to spread widely in aquatic ecosystems (Narayanan et al. 2022). Accumulation of PPCP micropollutants can lower the microbial population and eventually hamper the food chain. These micropollutants induce a hazardous impact on the biological

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Affect humans via food chain

PPCPs waste release in environment

Surfac -tants

UV filters

Phtha -lates

Antimicrobials

Fragrances

Antibiotics

Cause toxicity in aquatic organisms

Contamination of Aquatic ecosystem

Fig. 2 Release of PPCPs leads to contamination of aquatic ecosystem that can induce toxicity in aquatic organisms and via the food chain affect human health

system on long-term exposure (Li et al. 2019), even in minute concentrations (Krishnan et al. 2021), and are contemplated as crucial contaminants (Narayanan et al. 2022). The chronic as well as acute toxicity induced by PPCPs can alter normal biological processes in living organisms including humans, affecting their development and reproduction potential (Krishnan et al. 2021). Moreover, PPCP micropollutants can have genotoxicity in living organisms causing chromosome breaks, chromosomal aberration, and others, eventually influencing the structure and functions of aquatic systems (Narayanan et al. 2022). The PPCPs are endocrine disruptors, which obstruct normal functioning of the endocrine gland, consequently distressing health of organisms. The toxic effects of PPCPs in a mixture have been reported to induce synergistic impact, even at trace quantity, which implies that specific PPCP may have no substantial toxic effect, but when occurring in the presence of other pollutants, can induce a large impact at the same concentration (Narayanan et al. 2022). PPCPs can change the structure as well as the function of aquatic ecosystems by altering the behavior of organisms, the ability to form a primary biofilm, biogeochemical cycle, and growth, metabolism, and population dynamics of invertebrates (Hoppe et al. 2012; Richmond et al. 2016). Ciprofloxacin can affect functional attributes of leaf-associated microbial diversity, which could have a negative impact on microbe-mediated leaf decomposition, eventually affecting nutrient cycling in a stream (Maul et al. 2006).

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Pharmaceutical Contamination and Health Risk

The major concern related to pharmaceutical pollution stems from the fact that these goods are exclusively created to perform specific biochemical functions at small doses and target specific cell enzymatic, metabolic, and signaling activities (Kallenborn et al. 2018; Krishnan et al. 2021). These biochemical alterations may induce undesirable eco-toxicity in nontarget organisms after release in the environment (Kallenborn et al. 2018). Therefore, the existence of pharmaceutical micropollutants in ecosystems even in small quantity can cause substantial harm to nontargeted life-forms and the ecosystem (Krishnan et al. 2021). The repercussions of certain pharmaceutical ingredients on aquatic life have been presented in Table 1.

3.1.1

Antibiotic Resistance Development

Antibiotics are a crucial group of pharmaceuticals that are designed to treat diseasecausing microbial pathogens. The indiscriminate use of antibiotics introduces them as pollutants into the environment that can trigger antibiotic resistance in microorganisms, spread antibiotic resistance genes, and increase health risk (RodriguezMozaz et al. 2015; Okoye et al. 2022). Antimicrobial resistance (AMR) is a normal process that results in the development of resistance in pathogenic microorganisms against antimicrobial drugs, which consequently increases the infection persistence and abridges the ability to treat the infection (Goel et al. 2021). Through the analysis of various studies, it has been reported that the wastewater generated from hospitals contains higher number of pathogenic microorganisms with relatively high level of antibiotic resistance genes that may pose severe ecological threats (Ortuzar et al. 2022). The increased exposure to antibiotics has rapidly elevated the incidence of resistance development in pathogens against multiple drugs in the recent past (Mancuso et al. 2021). Therefore, in 2019, the World Health Organization (WHO) included AMR among the top ten threats to global health (Mancuso et al. 2021). It has been anticipated that more than ten million will die by 2050 due to AMR (Goel et al. 2021).

3.1.2

Impact on Reproductive Health

Pharmaceutical micropollutants in water have been found responsible for reversal of sex in male fishes, leading to feminization (Menon et al. 2020). Feminization in males is a condition where fishes display intersex and reproductive failure (KayodeAfolayan et al. 2022). Incomplete metamorphosis and limb deformation in aquatic organisms are other adverse reproductive impacts induced by pharmaceutical contaminants (Menon et al. 2020). These abnormal changes may gradually prompt extinction of various aquatic species. Sex hormones like estrogens are common environmental micropollutants that reached the aquatic ecosystem due to human

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Table 1 Eco-toxicity of PPCP contamination in aquatic ecosystem Pharmaceutical and personal care products (PPCPs) Diclofenac (nonsteroidal anti-inflammatory drug)

Organism (s) affected Salmo trutta fario (brown trout)

Cimetidine (antihistamine)

Aquatic invertebrates

Oxazepam (psychoactive drug)

Wild European perch Benthic bacterial community Daphnia magna

Triclosan (antimicrobial compound) Diclofenac, acetaminophen, and ibuprofen (nonsteroidal anti-inflammatory drug)

Amphetamine

Stream benthic organisms

Fluoxetine and citaloprama (antidepressant)

Aquatic invertebrates

Ibuprofen, diclofenac, and paracetamol

Danio rerio (zebrafish)

Ibuprofen

Rhamdia quelen

Effects Harmful effects on various organs were reported at concentrations that usually occur in environment Eliminated small-sized Gammarus fasciatus may be due to strong inhibitory effect on them or suppressed reproduction of adults. Abridged the growth as well as biomass of the adults. Moreover, high level of cimetidine significantly lowered Psephenus herricki survivorship Altered behavior and feeding rate at concentration of 1.8 mg/L

Reference Hoeger et al. (2005)

Increased resistance in bacterial diversity and modified their community composition All drugs displayed toxic effect but diclofenac exhibited the highest toxicity and acetaminophen displayed the lowest toxicity. Effects were time and concentration dependent. Low concentration was found to have lethal or sublethal effects, which could pose risk to nontarget organisms Altered communities of bacteria and diatoms in biofile, abridged autotrophic biofilm gross primary productivity, reduced Seston community respiration, and elevated population of dipterans Abridged biofilm gross primary productivity and community respiration Ibuprofen and diclofenac induced notable effects. These drugs significantly lowered the hatching rate at 55 hpf, reduced embryo locomotive, and were potentially neurotoxic Induced toxic effects on the kidney and displayed suppressive impact on immune system

Drury et al. (2013)

Hoppe et al. (2012)

Brodin et al. (2013)

Du et al. (2016)

Lee et al. (2016)

Richmond et al. (2016) Xia et al. (2017)

Mathias et al. (2018) (continued)

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Table 1 (continued) Pharmaceutical and personal care products (PPCPs) Caffeine and propranolola

Sertraline, paroxetine, fluoxetine, and mianserin

a

Organism (s) affected Diacyclops crassicaudis crassicaudis

Danio rerio (zebrafish)

Effects Propranolol was found toxic to D. crassicaudis crassicaudis, whereas caffeine does not display any toxicity. The mixture of both exhibits toxicity Abnormal embryo and larva development rate was elevated, hatching duration increased, and overall hatching rate was affected. Reduced hepatocyte proliferation in larva by threefold on exposure to all drugs and their mixture, except fluoxetine, was reported

Reference Di Lorenzo et al. (2019)

Nowakowska et al. (2020)

Used individually and in the mixture

consumption of oral contraceptives, and their minute contamination results in endocrine disruption in aquatic organisms (Santos et al. 2010). Estrogens are endocrine-disrupting compounds that mimic like steroid hormones or antagonize their activity (Jackson and Klerks 2020). Estrogens in fishes are involved in various activities including vitellogenin synthesis, secondary sexual characteristic development, and others (Santos et al. 2010). Presence of estrogen in water bodies lowers the viability and induces feminization or sterilization in fishes (Wedekind 2014). In particular, Heterandria formosa (killifish) exposed to 5 ng/L of 17-α-ethinylestradiol (EE2) from birth to 7 months displayed alteration in population dynamics (Jackson and Klerks 2020). The number of males, growth rate, and population size significantly declined and the sex ratio appeared to be female-biased (Jackson and Klerks 2020). Sun et al. (2019) in their study reported exposure of male Danio rerio (zebrafish) to 17-β-estradiol (E2) at both low and high concentrations which induced feminization and damage to gonads.

3.1.3

Behavioral Changes

Change in the behavior of aquatic organisms such as alteration in swimming pattern, feeding behavior, etc. is the result of exposure to toxic compounds like pharmaceuticals found in water ecosystem. The drugs containing psychoactive compounds have the capacity to instigate behavioral alterations in aquatic species (Cunha et al. 2017) such as change in swimming behavior and feeding performance of Japanese medaka (Nassef et al. 2010; Chiffre et al. 2016), increase diversion toward the anxiolytic drug in Danio rerio (Abreu et al. 2016), etc. The occurrence of psychoactive drug, e.g., oxazepam, in lower concentration in the water ecosystem was

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found to be associated with significant impairment in the feeding behavior of fishes (Kayode-Afolayan et al. 2022). Similarly, drugs like carbamazepine, fluoxetine, and diazepam improved positive phototactic behavior in Daphnia magna (Rivetti et al. 2016). Behavioral changes in organisms affect ecological functioning, as behavior is highly responsible for fitness of an individual, persistence of a population, interaction between species, species richness, and community composition (Brodin et al. 2014). Thus, increasing the concentration of pharmaceutical micropollutants is a sign of significant deterioration of aquatic ecosystem. And there is an urgent need for mitigation of micropollutant contamination.

3.2

Toxic Implications of Personal Care Product (PCP)-Related Micropollutants on Living Organisms

PCPs are sources of a variety of synthetic compounds into the environment such as surfactants (alkylphenol polyethoxylate), bisphenols, antimicrobial agents (triclosan), UV filters (zinc oxide, titanium oxide, homosalate), fragrances (galaxolide, celestolide), insect repellents like N,N-diethyl-m-toluamide (DEET), siloxanes, phthalates (dimethyl phthalate), and parabens (Molins-Dalgado et al. 2015; Khalid and Abdollahi 2021). These compounds after being released into the aquatic environment, even in trace quantity, induce negative impact on living organisms and alter ecological functions. Certain chemicals present in PCPs are lipophilic in nature and exhibit endocrine-disrupting properties that affect the reproductive system of aquatic organisms (Molins-Dalgado et al. 2015). Exposure of fishes to UV filters has been reported to induce alteration in hormone production and developmental abnormalities (Bluthgen et al. 2012; Gayathri et al. 2023). Similarly, release of antimicrobials in water from PCPs has raised the concern of inducing antibiotic resistance in aquatic microorganisms. For instance, exposure of adult male zebrafish and eleuthero-embryos to benzophenone-3 (UV filter) at low concentration resulted in downregulation of transcripts in testes, displaying antiandrogen activity (Bluthgen et al. 2012). Treatment of embryos or larvae of zebrafish with UV filter octocrylene at 50 and 500 μg/L lead to developmental toxicity, resulting in significant inhibition of acetylcholinesterase activity, oxidative stress, increased antioxidant activity, reduced heartbeat and hatching rate, and histopathological alterations (Gayathri et al. 2023). Triclosan, which is an antimicrobial agent used in PCPs, can be broken down into dioxin and induce detrimental effects of bacteria in aquatic ecosystem (Molins-Dalgado et al. 2015). Moreover, it can cause allergic sensation in children (Molins-Dalgado et al. 2015). Triclosan has been reported to exhibit weak estrogenlike property, and studies suggest that exposure to triclosan can affect the reproductive health of the aquatic organisms (Brausch and Rand 2011). For instance, triclosan was also found to be responsible for the alteration in the fin length and the sex ratio in medaka (Foran et al. 2000), inducing production of vitellogenin in male medaka after 21 days of exposure (Ishibashi et al. 2004) and reducing sperm count and

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vitellogenin synthesis in Gambusia affinis, 35 days after exposure (Raut and Angus 2010). The fragrances such as polycyclic musk and nitro musk are used in PCPs and have been reported to cause allergies like dermatitis, headache, and asthma (MolinsDalgado et al. 2015). Nitro musk, due to its potential to cause toxicity in aquatic organisms, is being phased out. Nitro musk and polycyclic musk have high octanol water coefficients and thus exhibit tendency to bioaccumulate in aquatic organisms (Brausch and Rand 2011). Contamination of water with PPCP micropollutants has been observed to exhibit the potential to induce harmful effects on aquatic life and other organisms including humans. Moreover, the emergence of AMR and loss of aquatic biodiversity are major issues of concern. Hence, there is an immediate need to regulate the introduction of PPCPs in water bodies and alleviate their accumulation.

4 Bioremediation: An Approach for Eliminating PPCPs from Aquatic Ecosystem The biodegradability of different PPCPs varies significantly; hence, WWTPs are often unable to remove such micropollutants, which eventually enter to the aquatic environment (Silva et al. 2019; Kujawska et al. 2022). Currently, several new techniques are being applied to remove PPCPs such as membrane-based technology, advanced oxidation, adsorption, and others (Kujawska et al. 2022; Priya et al. 2022); however, these approaches counter with challenges like high inputs of energy and chemicals that increase operational cost and elevate risks related to chemical use (Silva et al. 2019). Thus, there is a need to use a sustainable and economical approach that could eliminate or minimize PPCP pollution load from aquatic environments. Bioremediation is one of such potential methods that could be employed for the treatment of water-containing PPCPs (Couto et al. 2022). Bioremediation is an approach that employs the potential of living organisms, like plants, microorganisms, and/or their enzymes to remove pollutants from the environment and/or convert more toxic form either into the less toxic form or result in complete mineralization (Silva et al. 2019; Saha et al. 2021). Fungi, bacteria, and algae are the most potential candidates that can degrade the low and non-detectable levels of PPCPs in aquatic environments (Silva et al. 2019; Narayanan et al. 2022).

4.1

Potential of Fungi to Degrade PPCPs

Fungi are ubiquitous microorganisms that are found abundantly in both terrestrial and aquatic ecosystems (Vaksmaa et al. 2023). They are chemoheterotrophic organisms that can degrade a wide range of recalcitrant compounds by utilizing oxidative enzymes (Silva et al. 2019; Vaksmaa et al. 2023). Moreover, mycelia-bearing fungi

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due to their physiological and colonizing attributes can survive under harsh conditions (Silva et al. 2019). The white-rot fungi are observed to degrade different concentrations of PPCPs (Costa et al. 2019). These fungi can degrade lignin and other pollutants due to the presence of several catalytic enzymes (intracellular and extracellular enzymes including cytochrome P450 system, manganese peroxidase, and laccase), which also support degradation of pharmaceuticals such as ibuprofen, diclofenac, carbamazepine, norfloxacin, clofibric acid, atenolol, propranolol, and ciprofloxacin (Silva et al. 2019; Narayanan et al. 2022). The fungus Trametes versicolor can biodegrade sulfonamides and ofloxacin antibiotics (Narayanan et al. 2022). Trametes versicolor was discovered by Gros et al. (2014) to metabolize ofloxacin by 98.5% present in non-sterilized hospital wastewater sample via hydroxylation and oxidation and by cleavaging piperazine ring. Cruz-Morato et al. (2013) and Patel et al. (2019) demonstrated active transformation of seven pharmaceutical compounds from hospital effluent and up to 97% elimination of clofibric acid in 8 and 7 days of treatment, respectively, in a fluidized batch bioreactor by the action of fungi. The degradation or metabolization of PPCPs greatly varies in terms of time consumed depending upon the chemical structure of the compound, physicochemical properties, and capability of a microbe (Narayanan et al. 2022). For instance, T. versicolor was found to completely biodegrade erythromycin from water in 15 mins, whereas a reasonable amount of metronidazole and ketoprofen was transformed in 2 days of treatment (Pan and Chu 2016). The endophytic fungus Penicillium oxalicum B4 completely degraded 5 mg/L triclosan in 2 h, where initial concentration was reduced to 0.41 mg/L in 10 min (Tian et al. 2018). Three metabolites as breakdown residual products were reported which were confined to fungal mycelium and do not exhibit any sign of toxicity in Escherichia coli (Tian et al. 2018).

4.2

Role of Bacteria in Bioremediation of PPCPs

The PPCPs exhibit toxicity toward bacteria; nevertheless, certain bacterial species have capacity to degrade specific pharmaceuticals by utilizing them as nutrient sources (Narayanan et al. 2022). Once the complex structure of PPCP is broken down, further degradation into a less or nontoxic form can be carried out by the indigenous microbes (Narayanan et al. 2022). The bacterial strain F11 was found to biodegrade 7.5 μM antibiotic moxifloxacin present in wastewater, when supplied with acetate as a carbon substrate (Carvalho et al. 2016). Bacteria utilized antibiotic as a nitrogen source, leading to complete degradation and dehalogenation. Moreover, the biodegradation generated breakdown products that do not exhibit antimicrobial properties (Carvalho et al. 2016). Li et al. (2013) isolated Pseudomonas species from contaminated areas that are reported to degrade carbamazepine up to 47% via enzymatic digestion. Similarly, pharmaceuticals representing the sulfonamide group were degraded from 48% to 100% in 56 hours of treatment with Achromobacter denitrificans (Reis et al. 2014; Patel et al. 2019). Furthermore,

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Patel et al. (2019) found species belonging to genera Proteobacteria and Pseudomonas which are able to degrade sulfamethoxazole significantly from the aquatic ecosystem.

4.3

Improving the Efficacy of Microbial Agents Participating in Bioremediation

Microorganisms either individually or in consortium play instrumental roles in the removal of PPCPs from aquatic environments. Being an effective technique, bioremediation encounters several drawbacks. Bioremediation, involving microorganisms, is often influenced by factors such as availability of energy, existing environmental conditions like temperature and pH, physicochemical conditions of the reacting media and pollutants, inhibitory action of pollutants, presence of other chemical species, and competition with other living organisms (Fernandes et al. 2021; Narayanan et al. 2022). Any undesirable alterations in these factors affect the bioremediation potential, rendering fewer positive outcomes. These limitations can be overcome by utilizing microbial enzymes such as laccase, oxidoreductases, lipases, etc. in place of living microbes (Narayanan et al. 2023). Microbial enzymes facilitate degradation and removal of micropollutants and/or transformation of these substances into nontoxic form (Narayanan et al. 2023). In particular, laccase enzyme synthesized by the white-rot fungi is observed to degrade the micropollutants by the virtue of oxidation potential in phenolic as well as certain non-phenolic substances (Nguyen et al. 2020). Augmenting microbes with phytoremediators could improve the efficiency of PPCP bioremediation from the environment. For instance, combined application of fungus Pleurotus ostreatus and Zea mays significantly reduced galaxolide (fragrance) by 44.7%, and Phanerochaete chrysosporium-assisted phytoremediation (using Zea mays) alleviated 34.5% of tonalide (fragrance) in soil compared to initial content (Chane et al. 2023). Further, developing more resistant and high-potential genetically modified organisms can also orchestrate the bioremediation of PPCPs under unfavorable conditions. Genetic manipulation can result in development of microbes and/or their enzymes with desired traits and improved efficiency, leading to transformation or breakdown of targeted toxic compounds into nontoxic form (Narayanan et al. 2023; Vaksmaa et al. 2023). Bioremediation is an effective mechanism for degradation and elimination of PPCP micropollutants from the water ecosystem. Various naturally occurring microbial agents exhibit potential to partake in the process. However, the toxic nature of micropollutants, their concentration, and other factors can attenuate proliferation and efficiency of microorganisms. To overcome these challenges, indigenous microbial population augmentation with other efficient microbial biodegraders, introduction of microbial enzymes for PPCP degradation, combining phytoremediation with microbial remediation, and manipulating genetic material of microbes could encourage and speed up the removal process of toxic PPCPs from the environment. Moreover,

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construction of artificial wetlands containing phytoremediating plants could naturally improve microflora and mediate removal/degradation of PPCPs.

5 Conclusion and Future Recommendation The increase in human population and advancement in technology have elevated the production, consumption, and disposal of PPCPs in our environment. The extensive consumption of PPCPs to cure human and veterinary diseases and for personal grooming has escalated in the twenty-first century due to improved healthcare services and accessibility of such products. It has been anticipated that the trajectory of PPCP production and consumption will keep increasing in the future, adding more harmful micropollutants in the environment. Being persistent and toxic in nature, the introduction of such pollutants in aquatic environments can alter the natural structure and function of an aquatic ecosystem, eventually disturbing the ecological processes to a great extent. These disturbances not only influence the aquatic biodiversity but also exhibit detrimental impacts on humans, dwindling their health and survivability. To attenuate PPCP accumulation in the environmental matrix, particularly the aquatic environment, bioremediation is an effective, economical, and sustainable approach. In addition to focusing on approaches that function to eliminate PPCP residues from the environment, attempts should be made toward the attenuation of micropollutant introduction in the aquatic environment. The problem of PPCP pollution in the aquatic environment can be minimized by adopting the following approaches: 1. Setting guidelines and standards for the presence of different PPCPs in WWTP effluent, existing from the plant. 2. Incorporation of new techniques to enhance existing processes of WWTP, enabling removal of PPCPs as well as their metabolites. 3. Policies regarding the production and disposal of pharmaceutical products should be drawn to ensure safe disposal of unused and expired medicines. 4. More research should be done to extensively evaluate the occurrence, contamination level in various aquatic ecosystems, and toxicity risk of different PPCPs after short- and long-term exposure to different categories of living organisms.

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Organic Micropollutants in the Urban Soils: Technological Advances and Management Concerns Ravneet Kaur, Harleen Kaur, Swapnil Singh, Neetu Jagota, Ashutosh Sharma, and Ashish Sharma

Abstract Organic micropollutants simply known as micropollutants or emerging contaminants have become a serious concern for the environment because of their nature of entry into the environment and also due to their persistent nature. With anthropogenic activities at the heart of their production and introduction into the environment, these pollutants are so called due to their concentration found in nature which ranges from micrograms to picograms per liter or kg. These pollutants come from a variety of products that include personal care products (PPCPs), perfluoroalkyl and poly-fluoroalkyl substances (PFAs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), nanomaterials, steroid hormones, pesticides, plastics, and synthetic materials. One of the major concerns related to these compounds is their sources of existence in the environment that include groundwater, fresh water, soil, marine ecosystem, sediments, and dust. The occurrence of such substances in the environment can severely affect marine life, wildlife, and human societies. Therefore, knowledge about various micropollutants, their sources of production and introduction into the environment, and their effects on various life forms is of paramount importance. Hence, in the following chapter we will discuss about types of micropollutants, their occurrences and sources of production, and their effects on different life-forms. Keywords Agricultural wastes · Industrial wastes · Microplastics · Personal care products · Pesticides

R. Kaur · H. Kaur · S. Singh · N. Jagota · A. Sharma (✉) Department of Botany and Environmental Science, DAV University, Jalandhar, India e-mail: [email protected] A. Sharma Faculty of Agricultural Sciences, DAV University, Jalandhar, India © The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 R. Bhadouria et al. (eds.), Organic Micropollutants in Aquatic and Terrestrial Environments, https://doi.org/10.1007/978-3-031-48977-8_3

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1 Introduction Progress of the human society as a whole has resulted in the increase in people’s requirements considerably that eventually caused generation and buildup of harmful substances. Introduction and accumulation of these substances in air, water, soil, and food has severe damaging effects on the populations (Gavrilescu et al. 2014). Organic micropollutants (OMPs), also known as micropollutants or emerging contaminants, have become a significant concern in environmental science and public health in recent years owing to their persistence and the effects they show when they come in contact with the other organisms (Luo et al. 2014). These comprises chemical substances being released into the environment due to anthropogenic activities causing severe negative effects on living creature and ecosystem (Rehrl 2019). Understanding their origin and occurrence in the environment is crucial for assessing their risks and developing effective strategies for their management (Singh et al. 2021a). There are many ways to introduce these substances into the environments that encompass a variety of natural activities; however, human activities are one of the root causes for the introduction of these chemical compounds in the environment (Bertram et al. 2022). A number of human activities, primarily industrial processes, agriculture, and urbanization, have been the root causes for the production and use of a significant number of chemical substances. Where most of these compounds have been a boon for the society, certain compounds possess property of persistence and accumulation in living organisms (Asthana 2014; Rogowska et al. 2020). These persistent OMPs include some 20 classes of micropollutant substances such as pesticides, personal care products, pharmaceuticals, flame retardants, and industrial chemicals (Geissen et al. 2015). In order to monitor the occurrence, pathways of human exposure, and health issues associated with these compounds, micropollutants have been incorporated in the pathogen candidate list by the US Environmental Protection Agency (USEPA) (Khanzada et al. 2020). Organic micropollutants (OMPs) consist of a range of emerging pollutants, including pharmaceuticals such as hormones, antibiotics, analgesics, antiepileptics, cytostatic contrast agents, β-blockers, etc. Personal care products (PCPs) like antibacterial/disinfectant agents, perfumes, insect repellents, detergents, preservatives, and solar UV filters also fall under the category of OMPs (Kosma et al. 2010; Boxall et al. 2012). Also, many agrochemicals that include organochlorine and organophosphate insecticides, fungicides, and herbicides are also categorized as OMPs. Many other important industrial use products that include plasticizers and flame retardants are also responsible for producing OMPs (Luo et al. 2014). Organic micropollutants can enter into the environment through various pathways. Industrial discharges, improper waste management, agricultural runoff, and wastewater treatment plants are some of the predominant sources of these contaminants. Once released, they can enter surface water bodies, groundwater, soil, and even the atmosphere. Due to their persistence and mobility, organic micropollutants

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can travel long distances from their original source, leading to widespread contamination (Banzhaf and Hebig 2016; Rogowska et al. 2020). A large number of OMPs have been found in water bodies worldwide (Escher et al. 2014). Point sources are identifiable spots that contribute to pollution, while diffuse sources are more elusive and cover large geographical areas (Singh et al. 2021a, b). Occurrence of OMPs in the environment raises multiple concerns. Firstly, these substances have been found to have detrimental effects on aquatic ecosystems and can pose risks to human health upon consumption. Rogowska et al. (2020) have highlighted these impacts. Secondly, conventional wastewater treatment processes have limitations in effectively removing OMPs, leading to their release into the water supply. This situation exacerbates the challenges associated with OMP contamination, as mentioned by De Laender et al. (2016). Moreover, the increasing identification of OMPs in water sources is alarming due to potential long-term consequences for human health. Some of these substances have been associated with carcinogenic, mutagenic, and teratogenic effects, emphasizing the necessity for monitoring and mitigating their presence in the environment, as discussed by Bertram et al. (2022). By addressing these concerns, it becomes evident that the presence and persistence of OMPs in the environment necessitate comprehensive research and robust measures to safeguard ecosystems and protect human wellbeing. Given the aforementioned concerns, it is imperative to acquire a more profound comprehension of the sources and prevalence of organic micropollutants (OMPs) within the environment. By investigating their origins, transport mechanisms, fate, and behavior across various environmental compartments, scientists and policymakers can devise strategies to minimize their release, enhance water quality, and safeguard ecosystems and public health. Hence, the primary aim of this chapter is to observe and understand the emergence and occurrence of OMPs in the environment, emphasizing on their sources, pathways of release, and the extent of contamination. Additionally, we will explore the impact of these contaminants on the living creature and life-forms, aiming to mitigate the risks associated with OMPs, and ensure the protection of both the environment and human well-being.

2 Micropollutants Present in the Urban Environment Anthropogenic activities such as waste disposal practices or use of certain chemicals released by OMPs has become a serious matter of concern. The impact of these pollutants on biological systems is worrying, as they can affect important physiological processes related to behavior, reproduction, and communication in plants and animals. These pollutants can also be released into the atmosphere in various combinations of toxic substances. The presence of organic matter in the atmosphere was first highlighted by Altshuller and Buffalini et al. (1971). Pollution in general can be classified into three interrelated categories: newly created compounds that may be introduced into the environment, recently discovered preexisting pollutants

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present in the environment, and pollutants that have been categorized recently as hazardous for humans and the environment (Houtman 2010). Organic pollutants can exist in significant concentrations in soil and water. These pollutants, known as “emerging pollutants,” often come from urban, agricultural, and industrial wastewater sources. This represents a new paradigm, as many of these pollutants are created by industries but released into the environment for numerous uses, such as domestic, commercial, and industrial purposes. The concentration of emerging contaminants in water can range from nanograms to 10,000 nanograms per liter (ng/L), as measured in various studies (Boxall 2004; Esposito et al. 2007; Eggen et al. 2010; Clarke and Smith 2011; Diamond et al. 2011; Borgman and Chefetz 2013; Dalkmann et al. 2014). The so-called emerging pollutants have globally been recognized as an issue (Pal et al. 2010). The effect of their presence on the health of life-forms is mainly determined by the toxicity caused by them (Eljarat and Barcelo 2003). Toxic effects on algae, crustaceans, and fish from wastewater treatment plants (Vogelsang et al. 2006) have been commonly reported, and endocrine disruption in fish has been observed when water discharged from biological wastewater treatment plants (WWTPs) reaches rivers (Barber et al. 2015). Occurrence of estrogenic chemicals in the released wastewater has been the root cause of problems to aquatic life. Alkylphenols and synthetic and naturally secreted steroid hormones are often the main contributors to estrogenic potency (Song et al. 2022). However, other chemicals also exist that exhibit estrogenic potency which include phthalates, polybrominated diphenyl ethers, polychlorinated biphenyls, dibenzofurans, and pesticides (World Health Organization 2002). Most animals are incapable of fully metabolizing the majority of these compounds in vivo, resulting in the release of parent compound and their derivatives through feces (Carballa et al. 2004; Zhang et al. 2008). Similar careless treatment of antibiotics and their release in the environment without changing their molecular structure is another big problem (Sarmah et al. 2006; Kümmerer 2009) which have been frequently observed to enter the downstream wastewater treatment facilities and become absorbed in the freshwater supply and find their way into the food chains leading to damaging effects (Castiglioni et al. 2006; Lishman et al. 2006; Santos et al. 2007).

3 Air-Based Micropollutants Most of these chemicals are not easily broken down through natural processes. Only a small portion undergoes degradation. The remaining residues can attach themselves to soil and organic substances, evaporate into the air, or seep into groundwater. When agricultural runoff carries these residues and their byproducts into water sources, they pose a potential risk to drinking water (Stuart et al. 2012). Protecting the environment from air pollution caused by toxic organic micropollutants, such as polycyclic aromatic hydrocarbons (PAHs), pesticides, polychlorinated biphenyls (PCBs), and related compounds, is also an important goal. Therefore, it is necessary

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to take appropriate measures to address potential hazards from various sources, including workplaces, industries, power plants, vehicle emissions, agriculture, and other human activities. A specific challenge that is faced by the regulatory agencies in keeping track of the distribution and fate of micropollutants in the environment has been a substantial rise in the human activities due to urbanization and globalization (Thakur and Ganguly 2022). Presence of even traces of these organic compounds significantly impacts human health. Some compounds can produce pleasant aromas, savory flavors, and medicinal effects at appropriate concentrations. However, others can be fowl smelling or toxic when present above certain concentrations. Acute or chronic exposure to VOCs can cause respiratory distress, eye problems, and effects such as throat irritation, neurotoxicity, and cancer (Bala et al. 2021). VOCs can be removed by high surface area absorbents (Khan and Ghoshal 2000), which typically include activated carbon (AC) (Bradley et al. 2011). However, activated carbon is a granular or solid material that is often used for refilling columns than for other chores that require extensive handling to regenerate. Therefore, alternatives to ACs are desirable, especially products that combine good performance, ease of renewal, and easy integration into consumer products and/or textiles (Kim et al. 2013; Kayaci and Uyar 2014; Mallard et al. 2015).

4 Origin of OMPs in Urban Soil Typical grass topsoil contains approximately 10% organic matter, primarily derived from decomposing plant matter and teeming with microbial and animal life. Unfortunately, the soil has become a sink for significant amounts of synthetic organic compounds, some of which can resist degradation and be biologically active. The issue of pollution has shifted in recent years. Heavy metals in the atmosphere were a global concern 20 to 30 years ago, but the problem has now shifted eastward to countries like China, India, and Iran, where industrial and electrical development has outpaced measures to control pollution. Landfills and sewage are also significant sources of pollution, and oil and gasoline spills can contaminate the environment. In addition, organic solvents can accumulate to high levels in the environment (Singh et al. 2021a). Two groups of compounds that have received considerable attention due to their volatile nature are PAHs and PCBs. These chemically stable compounds are water resistant with extremely slow degradation (Zhang et al. 2007; Ma et al. 2009; Fabietti et al. 2010; Gupta et al. 2018). Incomplete combustion of organic materials mainly occurring in natural or human-caused fires forms the major PAHs source, while PCBs are purely of human origin (Cachada et al. 2012). According to Minh et al. (2006), many countries lack proper facilitations for disposing of municipal waste, resulting in poorly managed open dumps. Syed and Malik (2011) studied areas in Pakistan where factories and warehouses containing pesticides such as DDT were closed and found that surface runoff from these sites could contaminate soils and

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water bodies. Similar studies by other researchers have raised concerns about the potential health risks to people living in these areas (Agusa et al. 2003).

4.1

Occurrence of OMPs in Urban Soil

The soil’s function in urban environments is vital for the transportation and buildup of anthropogenic contaminants, as well as the transfer and distribution of persistent organic pollutants (POPs) within watersheds. Soils serve as reservoirs for pollutants, and various processes within soil affect the adsorption, retention, accumulation, distribution, and transfer of pollutants to rivers (Meijer et al. 2003). Soil pollution is majorly persuaded by anthropogenic activities such as land use, human activities such as agricultural inputs, industrialization, and watershed activity, as well as natural factors like erosion and the geochemical context. However, the primary source of soil contamination by OMPs is the agricultural use of TWW. This is because the soil is continuously irrigated from the crop growth period until the harvest period with TWW, while sludge is only applied periodically. Moreover, the soluble nature of OMPs in TWW makes them more mobile and bioavailable in the soil (Wu et al. 2015). On the contrary, sludge serves as both a source and a sink of OMPs owing to their organic matter content (Li et al. 2015; Wu et al. 2015; Fu et al. 2016). Organic micropollutants (OMPs) that originate from WWTPs undergo complex processes of adsorption, desorption, and transformation in soil. These processes depend on the physical and chemical properties of OMPs, properties of soil, and WWTP type used for irrigation (Christou et al. 2017). DOM composed of proteins, lipids, carboxylic and polycarboxylic acids, and polysaccharides and has the ability to interact with OMPs, competing with soil adsorption sites, thereby increasing the solubility and mobility of OMPs in soil. However, some research studies have also indicated that the interaction between DOM-OMP complexes and soil can lead to reduced mobility of OMPs in the soil (Graber and Gerstl 2011; Wu et al. 2015). Adsorption and desorption of OMPs in soil depend on specific interactions between the functional groups of OMPs, DOM in WWTPs, and soil organic matter (SOM) and hence largely depend on the properties of pollutants, WWTPs, and land (Chefetz et al. 2008). OMPs that find their way into wastewater and from there to soil is one of the major pathways for their transfer from one region to another. Additionally, soil gets polluted by human intervention by release of industrial wastes and products in the effluents which can enter into plants and from there into animals and humans when such plants are consumed.

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Uptake of OMPs by Plants

The distribution of contaminants in soil can occur through both aqueous and gaseous phases, and their uptake can occur by plants, interstitial water, or air. The physical and chemical properties of the pollutants as well as soil define the behavior of these pollutants in soil. Various compounds such as polychlorinated biphenyls (PCBs), dioxins (PCDDs), furans (PCDFs), and polycyclic aromatic hydrocarbons (PAHs) have been known to accumulate in plants from soil. Research on hydrophobic compounds such as PCBs, dioxins, and DDT has shown that these pollutants are mainly taken up by the roots and accumulate in lipid-rich tissues such as the skin of carrots, beets, and radishes. Pollutant transportation to other plant parts are supported by limited evidences. For instance, Hellström (2004) observed no transfer of phenolic compounds or PAHs from barley grains to soils treated with two contaminated fertilizers. The accumulation of organic pollutants in crops and the contamination of agricultural land pose a significant risk to human health. There have been studies on the uptake of environmental pollutants in sludge or compost, as reported by Tripathi et al. (2020).

5 Origin of OMPs in Water One of the major concerns of recent times is the contamination of surface waters by micropollutants. WWTPs release micropollutants, including untreated wastewater, into rivers, lakes, streams, and reservoirs. These compounds can either be transported with the water to different locations or they may accumulate in sediments. Although some micropollutants can be chemically and biologically degraded by surface waters, they can persist and accumulate (Singh et al. 2021b, c). Large cities are particularly vulnerable to water pollution from domestic wastewater (Monre 2010). For instance, Ho Chi Minh City (Gso 2013) releases 413,000 cubic meters of wastewater per day. Water pollution is the issue both in rural and urban areas, with pesticide and fertilizer residues being the primary cause of contamination in rural areas (Chau et al. 2018). Emerging pollutants, including regulated and unregulated organic pollutants, have been detected in surface water as well as groundwater at concentrations ranging from n to n × 105 ng/L (Masoner et al. 2014). Anthropogenic activities are one of the significant reasons for the introduction of these compounds into surface water as well as groundwater (Khatri and Tyagi 2015). Many countries have realized the seriousness of the issue related to the existence of PCBs and PAHs in the environment and are putting in effort to study the same (Reyes et al. 2003; Cardellicchio et al. 2007; Wade et al. 2008; Zheng and Vista 1997). In recent times, there has been increasing concern about the occurrence of several micropollutants in urban aquatic environments (Fent et al. 2006; Schwarzenbach et al. 2006). Such micropollutants, although present in low

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concentrations, are very harmful. They primarily enter the environment via discharge into domestic sewage systems (Osenbrück et al. 2007). This applies not only to household products, and various chemicals in food or textiles, but also to drugs and their metabolites being present in urine and feces. The contamination of municipal wastewater is not limited to domestic pollutants but also includes heavy metals, pesticides, and hydrocarbons that leach into runoff from urban areas such as roads, buildings, parks, and gardens (Margot et al. 2015). In many countries, the principal source of drinking water is surface water especially in areas where urban populations are rapidly expanding. This implies that drinking water may get contaminated with these pollutants which can make their way into water treatment plants through surface waters. Various researchers have reported the presence of micropollutants in tap water, including clofibric acid concentrations exceeding 165 ng/L in Berlin. This means that people may unknowingly be exposed to these micropollutants through consumption, cooking, and bathing with tap water. Therefore, it is crucial to remove micropollutants during water treatment to produce safe drinking water. However, the presence of micropollutants in tap water implies that current water treatment systems cannot completely remove them from drinking water (Kim and Zoh 2016).

5.1

Occurrence of OMPs in Aquatic Environments

The existence of micropollutants in aquatic ecosystems has become a significant global environmental issue in recent years. These emerging pollutants consist of a diverse range of natural and human-made substances (Luo et al. 2014). To identify the pollutants that require more attention, it is mandatory to understand the spatial and temporal distribution of these compounds. By considering the specific properties of these compounds and environmental factors, we can better understand their behavior in the environment, which is crucial for developing quality standards and regulations. Commonly detected compounds in surface waters include carbamazepine, diclofenac, ibuprofen, and caffeine (Luo et al. 2014). Other frequently detected compounds include bezafibrate, iopromide, tramadol, azithromycin, etc. (Ebele et al. 2017; Yang et al. 2017). The presence of micropollutants in aquatic environments is an environmental issue globally, as these substances, whether of human origin or naturally occurring, can enter water sources and pose a threat to wildlife and the drinking water industry. Micropollutants cause several detrimental effects, such as short- and long-term toxicity, disruption of endocrine functions, and antimicrobial activity. The potential impacts on human and ecological health due to micropollutant exposure have gained significant attention in recent years. Several studies have highlighted the harmful effects that can arise from chronic exposure to complex mixtures of micropollutants. Wastewater serves as the primary source of several micropollutants, and traditional wastewater treatment systems may not be fully effective in their removal.

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Consequently, micropollutants can find their way into water sources, posing risks to both life-forms and the environment. The concentration of micropollutants in both incoming waters and treated wastewater effluents shows significant variations in space and time due to various factors, including production rates, consumption practices, excretion rates, size and efficiency of treatment plants, and persistence in the environment (Luo et al. 2014). Additionally, weather conditions like temperature and sunlight can affect the liberation of micropollutants from WWTPs. Many other sources consider wastewater discharge from treatment plants to be the principal source of water contamination (Kasprzyk-Hordern et al. 2009). After treatment, micropollutants undergo varying degrees of natural attenuation, such as dilution in surface waters, adsorption on suspended solids and sediments, direct photolysis, and aerobic biodegradation (Pal et al. 2010). Micropollutants were found to increase during dry weather but decrease significantly during wet weather. There exists seasonal variation in the occurrence of drug levels in water, which increases more in winter than in summer (Wang et al. 2011). Increased biodegradation and/or higher dilution during summer months could be responsible for this. However, precipitation does not help in reduction of micropollutant level, as demonstrated in studies by Jungnickel et al. (2008), Sakamoto et al. (2007), Schoknecht et al. (2009), and Singer et al. (2010). Micropollutants are more prevalent in surface water than in groundwater, as reported by Loos et al. (2010). Certain regions, particularly in some parts of North America and Europe, exhibit a notable presence of micropollutants in groundwater. The contamination of groundwater with micropollutants primarily occurs through various mechanisms, such as leachate from landfills, the interaction between groundwater and surface water, infiltration of polluted water from agricultural areas, and seepage from septic tanks and drainage systems. Concentrations of micropollutants in landfill leachate and septic tank wastewater generally range from 10 to 104 ng/L and 10 to 103 ng/L, respectively (Lapworth et al. 2012). Pesticides and other toxic substances are often introduced into the soil, making it a major source of micropollutants (González-Rodríguez et al. 2011). Bulk pharmaceuticals and personal PPCPs can also be removed from the soil, but the rates of removal can vary depending on the specific compounds and the methods used for measurement (Onesios et al. 2009). Furthermore, different studies may define “removal” or “elimination” rates differently and may use different sampling methods (such as embedded vs. captured samples), making direct comparison challenging (Ratola et al. 2012).

5.2

Mechanisms of Uptake and Transport of OMPs in Plants

The uptake and translocation of OMPs by plants involve their penetration into different layers of the root system, including the epidermis, cortex, endodermis, and Casparian strip, followed by transport through the vascular system (i.e., phloem and xylem). The charge of the molecule plays a crucial role in this absorption

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process. Anionic OMPs are expected to have a lower absorption rate than cationic OMPs due to the negative potential of the plant cell membrane, which causes repulsion between the negatively charged OMPs. Cationic OMPs, on the other hand, can be attracted to biofilms and other ionic interaction mechanisms, which can increase their absorption rate. Neutral molecules are generally absorbed faster and transported more easily through the phloem and xylem than ionic molecules (Wu et al. 2015; Al-Farsi et al. 2017). The polarity and charge of OMPs also have an impact on their fate in plants. Hydrophobic compounds tend to accumulate in the lipid fraction and are retained by the roots, while hydrophilic compounds are more easily transported through the xylem to the aerial parts (Bartrons and Peñuelas 2017). The soil solution and its OMP concentration are also relevant factors for pollutant absorption by plants. The interstitial water OMP ratio is the most effective for plants and is strongly correlated with the absorption ratio (Li et al. 2019). Table 1 lists the sources of OMPs.

6 Conclusions and Future Prospects Organic micropollutants (OMPs) cause a significant threat to the environment, including the soil, air, and water (both surface water and groundwater). These pollutants stem from various sources, including wastewater, agriculture, hospitals, and household products. Their negative effects can also extend to human health. It is important to gain a better understanding of the micropollutants’ fate and to develop effective models to predict their impact on the environment. Toxic substances utilized in agricultural practices can also harm crops and plants, further contributing to soil and water pollution. Reducing the usage of pesticides, insecticides, herbicides, plastic products, and other harmful substances can help to minimize organic micropollutant pollution. Additionally, wastewater treatment plants can aid in removing OMPs from water and other environmental components. Therefore, dealing with the issues related to OMPs in the environment, a multifaceted approach is needed that will include and combine regulation, treatment, monitoring, pollution prevention, and cooperation of various agencies. On induction of such an approach, a system can be developed that will minimize the release of OMPs in the environment and help in its protection. Based on the understanding of origin and occurrence of OMPs in the environment, the following points can be emphasized in the near future: • The information generated from studying the OMPs should be used to exercise control and propose stricter measures for release of these compounds into the environment or it can be proposed to use less harmful compounds. • Monitoring and assessment programs should be launched to assess the existence of these compounds in the environment. • Practices should be inculcated to control these compounds at their source and strategies for pollution prevention should be designed.

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Table 1 Occurrence of micropollutants in the environment and their sources of emergence Micropollutants Fungicide Motor oil and lubricant combustion products

Sources

References

Landfill sites

5-Fluorouracil (cytostatic) Propofol Platinum

Hospital waste Anesthesia biproducts Tumor and other cytostatic therapy products From antibiotics and diuretics From MRI waste Disinfectants Bottom sediments of sea water

Hollender et al. (2008) Verlicchi et al. (2010)

Mercury Gadolinium Alcohols and aldehyde mixtures Heavy plastics (polyvinyl chloride) Persistent organic pollutants (POPs) Plastic resin pellets (PRP) Polyethylene (PE) pellets Triclosan Nonylphenol Sucralose Pharmaceuticals Acetaminophen Caffeine Ibuprofen Naproxen Salicylic acid Fungicide: Organic solvents and pesticides

Industrial waste, raw material from plastic products

Toxic chemicals like HCHs, DDTs, PCBs, and PBDEs Vinyl chloride, methylene chloride

Agriculture industry and domestic use products Chlorinated toxic byproducts

Point pollution Nonpoint pollution

Livestock factories Farm lands and abandoned mines Farming and factory wastes Medicines and daily use products

Herbicide and pesticide residues Beta-blockers, anti-inflammatory drugs, contraceptives, antibiotics, neuroactive compounds, etc. Hexachlorobiphenyl

Endocrine-disrupting chemicals

Polycyclic aromatic hydrocarbons

Hirai et al. (2011) Mizukawa et al. (2013)

Household chemicals

Qi et al. (2014)

Commonly found in wastewater treatment plants and their effluents

Luo et al. (2014)

Agriculture and industry

Maier and Gentry (2015) Bartrons et al. (2016) Lin et al. (2017) Singh et al. (2020)

Anthropogenic (transformers, capacitors, hydraulic fluids, cutting oil) Waste from farming activities, animal husbandry, household, and sewage Burning of fossil fuels and direct storage of oil and petroleum product

Gautam and Anbumani (2020) Gupta et al. (2020) Ghose and Mitra (2022) Gasperi et al. (2022)

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Schoknecht U, Gruycheva J, Mathies H, Bergmann H, Burkhardt M (2009) Leaching of biocides used in façade coatings under laboratory test conditions. Environ Sci Technol 43:9321–9328 Schwarzenbach RP, Escher BI, Fenner K, Hofstetter TB, Johnson CA, Von Gunten U, Wehrli B (2006) The challenge of micropollutants in aquatic systems. Science 313:1072–1077 Singer H, Jaus S, Hanke I, Lück A, Hollender J, Alder AC (2010) Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water. Environ Pollut 158:3054–3064 Singh J, Yadav P, Pal AK, Mishra V (2020) Water pollutants: Origin and status. Sensors in water pollutants monitoring: Role of material 5:20 Singh VK, Chaudhari AK, Notarte KIR, Kumar A, Singh R, Bhadouria R (2021a) Metal-oxidizing microbes and potential application in bioremediation. In: Microbe mediated remediation of environmental contaminants. Woodhead Publishing, pp 107–114 Singh P, Singh R, Verma P, Bhadouria R, Kumar A, Kaushik M (2021b) Plant-MicrobesEngineered Nano-particles (PM-ENPs) nexus in agro-ecosystems Singh VK, Singh R, Kumar A, Bhadouria R, Pandey S (2021c) Sewage wastewater and sludge as source of traditional and emerging contaminants in agroecosystems. Sustainable Agriculture Reviews 50: Emerging Contaminants in Agriculture: 35–59 Song J, Zhao J, Yang C, Liu Y, Yang J, Qi X, Li Z, Shao Z, Wang S, Ji M, Zhai H (2022) Integrated estrogenic effects and semi-volatile organic pollutants profile in secondary and tertiary wastewater treatment effluents in North China. JHM Letters 435:128984 Stuart M, Lapworth D, Crane E, Hart A (2012) Review of risk from potential emerging contaminants in UK groundwater. Sci Total Environ 416:1–21 Syed JH, Malik RN (2011) Occurrence and source identification of organochlorine pesticides in the surrounding surface soils of the Ittehad Chemical Industries Kalashah Kaku, Pakistan. Environ Earth Sci 62:1311–1321 Thakur D, Ganguly R (2022) Occurrence and fate of micropollutants in air. In: Environmental micropollutants. Elsevier, pp 305–313 Tripathi S, Singh VK, Srivastava P, Singh R, Devi RS, Kumar A, Bhadouria R (2020) Phytoremediation of organic pollutants: current status and future directions. Abatement Environ Pollutants 81–105 Verlicchi P, Galletti A, Petrovic M, Barceló D (2010) Hospital effluents as a source of emerging pollutants: an overview of micropollutants and sustainable treatment options. J Hydrol 389:416–428 Vogelsang C, Grung M, Jantsch TG, Tollefsen KE, Liltved H (2006) Occurrence and removal of selected organic micropollutants at mechanical, chemical and advanced wastewater treatment plants in Norway. Water Res 40:3559–3570 Wade TL, Sweet ST, Klein AG (2008) Assessment of sediment contamination in Casco Bay, Maine, USA. Environ Pollut 152:505–521 Wang C, Shi H, Adams CD, Gamagedara S, Stayton I, Timmons T, Ma Y (2011) Investigation of pharmaceuticals in Missouri natural and drinking water using high performance liquid chromatography-tandem mass spectrometry. Water Res 45:1818–1828 World Health Organization (2002) Global assessment of the stateof- the-science of endocrine disruptors. In: Damstra T, Barlow S, Bergman AA, Kavlock R, Kraak Gvd (eds) Report No. WHO/PCS/EDC/02.2, The International Programme on Chemical Safety, Geneva, Switzerland. http://www.who.int/ipcs/publications/endocrine_disruptors/en/ Wu X, Dodgen LK, Conkle JL, Gan J (2015) Plant uptake of pharmaceutical and personal care products from recycled water and biosolids: a review. Sci Total Environ 536:655–666 Yang Y, Ok YS, Kim KH, Kwon EE, Tsang YF (2017) Occurrences and removal of pharmaceuticals and personal care products (PPCPs) in drinking water and water/sewage treatment plants: a review. Sci Total Environ 596:303–320

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Part II

Effects of Organic Micropollutants on the Environment and Human Health

Assessment of Environmental Pollutants for Their Toxicological Effects of Human and Animal Health M. V. N. L. Chaitanya, Smriti Arora, Rashmi Saxena Pal, Heyam Saad Ali, B. M. El Haj, and Rajan Logesh

Abstract An environmental pollutant is any material that is present in the environment and is hazardous to humans or the lives of any living species but is necessary for human existence and well-being. This chapter focuses on environmental chemical and agricultural pollutants (ECPs and EAPs) comprising either organic or inorganic materials. Chemical pollutants can be both natural and man-made, and they are mostly found in the air, water, and soil. Natural ECPs can occasionally be caused by naive or reckless human behavior. The bulk of ECPs are man-made and the product of human activities striving to improve life quality through industrialization. All ECPs can be harmful to human health because they are risk factors for diseases ranging from respiratory difficulties to cancer. Additionally, some ECPs, such as carbon dioxide, are released into the atmosphere as a result of industrial activity, which may indirectly negatively influence the life on Earth by contributing to global warming. Unlike natural ECPs, government regulation can limit or even prevent synthetic ECP production. The ECP cleanup is challenging and costly from an economic standpoint and necessitates highly specialized knowledge. Pesticides, toxic farm chemicals, and fertilizers are some of the most widespread EAPs. Pollution of the air, water, soil, and marine environments is just the beginning; M. V. N. L. Chaitanya (✉) · R. S. Pal School of Pharmaceutical Sciences, Lovely Professional University, Phagwara, Punjab, India S. Arora Department of Allied Health Sciences, School of Health Sciences and Technology, University of Petroleum & Energy Studies, Dehradun, Uttarakhand, India e-mail: [email protected] H. S. Ali Department of Pharmaceutics, University of Khartoum, Khartoum, AI Khartoum, Sudan B. M. El Haj Department of Pharmaceutical Chemistry, University of Science and Technology of Fujairah, Fujairah, UAE R. Logesh Department of Pharmacognosy, JSS College of Pharmacy (JSS Academy of Higher Education and Research), Mysuru, Karnataka, India e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 R. Bhadouria et al. (eds.), Organic Micropollutants in Aquatic and Terrestrial Environments, https://doi.org/10.1007/978-3-031-48977-8_4

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these contaminants also pose a threat to human health through the plants and animals that humans eat. It has been noted that EAPs can cause hormonal disruptions in both animals and humans, and crop exposure to various contaminants in high quantities from air and water will result in reduced yields and growth and early mortality of plants. The economic impact of EAPs is represented in the costs of remediation and disease treatment caused by them. The current chapter focuses on the important environmental pollutants and their various biological or toxicological impacts on human and animal health. Keywords EAPs · ECPs · Environmental Protection Agency · Health impact · Pollutants

1 Introduction An environmental pollutant is any substance that is found in the environment and is harmful to humans or to the life of any living species that is deemed useful to human’s survival and well-being. The environment is everything that surrounds us (air, water, soil) whether we are in our homes, places of study, work, or recreational activity. Therefore, whatever that affects the environment will have a positive or negative impact on us. Possibly, this has been the case since the beginning of life on planet Earth. In 1800, the world population was only one billion people; in 2022, it is eight billion people. The world has not increased in size to accommodate the extra seven billion people since 1800 (Lodeiro et al. 2021). There has been a lot of research on how people interact with their environments because of all the ways in which our species can alter the natural world. Both biotic (organisms and microbes) and abiotic (nonliving) factors interact to create what we call the environment (hydrosphere, lithosphere, and atmosphere). It is generally agreed that pollution occurs when substances that are damaging to humans and other forms of life are released into the environment. The increased concentrations of dangerous solids, liquids, or gases are what we call pollution, and they have a negative impact on our ecosystem. All three of these resources—water, air, and soil—are negatively impacted by human activity (Singh et al. 2021). While the Industrial Revolution enhanced our access to contemporary amenities such as electricity and transportation, it also resulted in the release of hazardous amounts of air pollution, which has had a significant impact on human health. People worldwide recognize that ecosystem contamination endangers human health. This essential topic is connected with societal standards, economic issues, the law, and human behavior. Anthropogenic air pollution is one of the most serious public health issues, causing about nine million deaths each year, and it is undeniable that urbanization and industrialization have reached unprecedented and scary levels around the world in our time (Manisalidis et al. 2020). Between 1760 and 1820–1840, the Western world witnessed the earliest stirrings of the modern industrial period. The success of the Agricultural Revolution, an availability of coal, favorable political conditions, and the country’s physical setting were some of the

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factors of the Industrial Revolution. The Industrial Revolution brought with it advancement and improvement in many parts of life, but it also had severe consequences in others, particularly those harming the environment. Deforestation, loss of many animal species due to illicit hunting, and pollution of the ecosystem all have detrimental consequences. Deforestation is rightly or wrongly justified by availing more residential areas or big energy production projects, by building houses, and as source of heat energy. Some animals are hunted for use of some of their parts in the manufacture of accessories. Considerable damage to the environment comes from its pollution mainly by substances resulting from industrialization (Tian et al. 2023). Pollutants in the environment have unexpected consequences because they impair plant, animal, and human life either instantly or indirectly through the food chains on which they rely. As environmental pollution is a global burden, UK’s plan to bury carbon dioxide in the North Sea is a fascinating case study in the elimination, containment, and even beneficial reuse of a potentially hazardous chemical. The 2035 target for the UK government to eliminate carbon emissions from energy generation includes the construction of carbon capture power stations. Oil and gas reserves can be tapped by using captured CO2 that has been stored for later use. There is a dire need for new, creative approaches to the problem of chemical pollution and the potential reuse of these substances. It is our hope that the EPA would take the initiative in this matter (Wang et al. 2020). The different kinds of environmental chemical pollutants (ECPs) and their impacts on human health, including their mutagenicity, carcinogenicity, teratogenicity, and immunotoxicogenicity, are discussed in this chapter.

2 Environmental Chemical Pollutants (ECPs) Environmental chemical pollutants (ECPs) can be created from a wide variety of organic and inorganic components. Unfortunately, whether natural or artificial, irresponsible humans can contribute to the emergence of natural ECPs. Man-made ECPs, which are the majority, result from human activity seeking to improve life quality via industrialization. All the ECPs can be detrimental to human health by being risk factors for diseases extending from respiratory problems to cancer. One thing that can indirectly harm Earth’s biota is carbon dioxide (CO2), released into the environment by automotive exhausts and other industrial activities (Chormare and Kumar 2022). Natural organic ECPs include polycyclic aromatic hydrocarbons (PAHs) of which only naphthalene (with two fused benzene rings) is man-made. Man-made organic ECPs include polychlorinated biphenyls (PCBs) and tributyltins (TBTs) (Fig. 1). Carbon monoxide (CO) gas may be considered as latent ECP generated from fires caused by poor human activity. Heavy metal ions are another source of ECPs resulting from anthropogenic activity (Barbosa et al. 2023). Some of the ECPs are described below:

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3

2

2'

4

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CH3

3' 4'

5

6

6'

5'

O

Cln

Polychlorinated biphenyls

Sn

Sn

CH3 CH3

CH3 CH3

Tributylines

Fig. 1 Polychlorinated biphenyls and tributyltin

2.1

Polycyclic Aromatic Hydrocarbons (PAHs)

While many PAHs are known to be carcinogenic, only five have been identified as environmentally persistent pollutants because of their ability to accumulate in biota and food chains and hence stay in the environment, and these five PAHs are important (Mojiri et al. 2019) (Fig. 2). According to the Water Framework Directive (WFD) and the European Quality Standards Directive (EQSD) (2008/105/EC as amended by 2013/39/EU), these are priority hazardous substances ubiquitously present, bioaccumulative, and toxic (uPBT) compounds. Since they have no known industrial or otherwise uses, PAHs are not intentionally produced. However, they occur naturally in the environment as by-products from different sources including industrial sources: power generation, cement manufacturing, coke production and burning, and rubber/tire manufacturing and burning (Filippi et al. 2022). PAHs are also found in fossil fuels like coal and oil and road-building materials like bitumen. Combustion releases most PAHs and PAHs are released into the atmosphere by home wood burning. 84% of atmospheric load is domestic combustion. PAHs emitted to the atmosphere can enter the aquatic environment through atmospheric deposition to surfaces and runoff during rainfall. Automobile transit contributes about 3%. Cost-effective energy solutions can solve the residential combustion energy dilemma (Yilmaz et al. 2022).

Benzo[a]pyrene

indeno(1,2,3-cd)preen

benzo[k]fluoranthene

benzo(g,h,i)perylene

benzo(b)fluoranthene

Fig. 2 Polycyclic aromatic hydrocarbons (PAHs) as pollutants

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Considerable amounts of toxic PAHs may be introduced into the lungs of cigarette smokers with the possible consequence of carcinogenesis and the immense cost of treatment. The high hydrophobicity and low water solubility contribute to the deposition properties of PAHs. PAH pollutants may be detrimental to different forms of life through mutagenicity, carcinogenicity, teratogenicity, and immunotoxicogenicity. PAHs are hazardous environmental pollutants released into the environment as a result of rapid industrialization and urbanization (Carpenter 2006).

2.2

Polychlorinated Biphenyls (PCBs)

Polychlorinated biphenyls (PCBs, Fig. 1) are synthetic organic aromatic compounds containing the elements of carbon, hydrogen, and chlorine. They have wide industrial applications. Their preparation started in 1929 and ended in 1979 upon a ban imposed by the Environmental Protection Agency (EPA) because they were considered hazardous anthropogenic environmental pollutants (He et al. 2021).

2.3

Fluorocarbons and Chlorofluorocarbons

Carbon-fluorine combinations, known as fluorocarbons (FCs), are powerful greenhouse gases that can build in the environment, primarily in the air due to their nature as gaseous products, but also in water, soil, and the food chain through infiltration. Due to their chemical resistance and longevity, fluorocarbons are used in stain repellents, nonstick cookware, and coolants. Stability is a benefit and a drawback of chlorofluorocarbons (CFCs), which are banned worldwide due to their ozonedepleting effects and the Montreal Protocol. Environmentally harmful halocarbons may vary. Scientists are developing a catalytic approach to reduce fluorocarbons’ toxicity by separating carbon and fluorine (Briffa et al. 2020). However, because of the nature of the application surface (the atmosphere) and cost of the materials needed in the process, the method may not prove to be financially rewarding. The structurally related chlorofluoromethanes are used as refrigerants, propellants, and solvents. However, because of their damaging effects on the ozone layer, they are now being phased out and replaced by hydrofluorocarbons.

2.4

Heavy Metals as Environmental Pollutants

Heavy metals are a concern not only for the environment but also for human health. And they are an important concern despite the fact that they are not organic pollutants but rather the primary contaminants because of their widespread use in

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industry, households, agriculture, medicine, and technology. Although invisible to the naked eye, ions play a crucial role in maintaining life, and they are one of the many types of metallic contaminants. Thallium, uranium, vanadium, and silver have no established biological functions and are highly toxic to humans, as are the heavy metals cadmium (Cd), lead (Pb), arsenic (As), and mercury (Hg). Among the heavy metals, mercury stands unique since it is toxic in its elemental form, inorganic salt form, and organic form known as methylmercury. With the exception of mercury (Hg), metals exert their biochemical, physiological, and toxicological effects when they are in ionic forms (i.e., as inorganic compounds). Unlike elemental forms of metals, ionic forms are water soluble and hence can be absorbed systemically to exert their effects, toxic or otherwise (Rahman and Singh 2019).

2.4.1

Origins of Pollutant Heavy Metals in the Environment

• Heavy metals enter soil and groundwater through several pathways: atmospheric deposition, leaching, soil erosion of metal ions, corrosion, resuspension of sediment, and evaporation from water resources (Hong et al. 2012). • Weathering and volcanic eruptions are two examples of natural occurrences (Bensefa-Colas et al. 2011). • Methylmercury, a naturally occurring compound found in fish and shellfish (Azevedo et al. 2023). Human activities such as metal mining, refining, smelting, casting, consuming, and using these materials in the home and on farms are the primary causes of environmental degradation and the resulting health risks to humans (Tchounwou et al. 2012). Many different types of manufacturing facilities can be considered industrial sources, including but not limited to those involved in metal refining (metallurgy), coal-fired power plants, nuclear power plants, petroleum combustion, high-tension power lines, textiles, plastics, wood preservation, microelectronics, and paper processing. As, Cd, Cr, Pb, and Hg are naturally occurring heavy metals which become pollutants due to human activities. These metals are systemic toxicants that have been linked to a wide range of deleterious human health effects, including developmental abnormalities, neurologic and cardiovascular diseases, neurobehavioral problems, hearing loss, diabetes, hematologic and immunologic disorders, and cancer (Saleha et al. 2001). The duration and severity of health problems induced by heavy metals vary on the metal, its chemical form, the amount of exposure, and the length of time after exposure began. Most people are exposed through ingestion, inhalation, or skin contact. The toxicokinetic and toxicodynamic properties of metals are highly dependent on their particle size, solubility, valence state, chemical form, and biotransformation (Tchounwou et al. 2003). Exposure to high amounts of dangerous metals in one’s regular environment has been associated with an increased risk of a wide range

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of health problems. The immediate and long-term effects of exposure to toxic metal combinations are largely unknown, despite the vast study on the effects of exposure to individual metals. New research shows that these toxins can interfere with the body’s ability to process iron, calcium, copper, and zinc. The presence of multiple heavy metals may result in additive, antagonistic, or synergistic effects. Due to their essential role in so many facets of human life, metals (apart from the dangerous ones) may be permitted to exist in the environment without regard to their source. Cleaning up the environment might lessen the severity of hazardous metals’ adverse health impacts; hence, bioremediation of heavy metals from organic food and water is very important (Sutton and Tchounwou 2007). The bioremediation techniques of heavy metals are discussed below:

2.4.2

Bioremediation of Heavy Metals by Microorganisms

The use of algae, bacteria, fungi, or plants to decrease and/or recover heavy metal pollution into less harmful forms is known as bioremediation, and it is a novel approach to cleaning up contaminated environments. Heavy metals in polluted water supplies and soils have been eliminated with this method. The employment of microbes is an important part of heavy metal cleanup, and this strategy is an attractive alternative to physical and chemical approaches. Microorganisms used in remediating polluted settings have similar long-term environmental benefits and cost-effectiveness and are also sustainable (Bhadouria et al. 2020). The presence of these organisms aids in the elimination of potentially harmful substances. It can operate normally, or it can be boosted by adding electron acceptors, nutrients, or something else to the mix (Tripathi et al. 2020). The valence transformation mechanism can be used for detoxification purposes because of the varying toxicity of metals across their valence states, and this is a very relevant consideration for them. The bacteria that are resistant to mercury produce an enzyme called organomercurial lyase, which transforms methyl mercury to Hg(II), which is one hundred times less harmful. Lot of research has been carried out on the process by which Cr(VI) is converted to Cr(III), a form that was less mobile and hazardous (Dixit et al. 2015). Metal binding, vacuolar segregation, and evaporation also contribute to heavy metal detoxification. Metal ions were made more readily available for uptake and transport by microbes with the help of chelators like phytochelatin and metallothionein. Metal binding, vacuole compartmentalization, and volatilization are all methods of heavy metal detoxification, and they’ve all been studied extensively because of their role in converting Cr(VI) to Cr(III), a form that is less mobile and harmful. Metal chelators, like phytochelatin and metallothionein (a peptide derived from glutathione), bind metal ions, making them easier for bacteria to take up and transfer. Only Se and Hg have sufficiently volatile states to perform this type of chelation, and mercury-resistant bacteria use the MerA enzyme to convert Hg (II) to the volatile form Hg (I). It has been utilized in water and soil purification to convert Se(V) to Se(0) (Balzano et al. 2020). These organisms’ metabolic processes aid in the conversion of environmental pollutants. The Se(V) to Se(0) reduction has

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been used in water and soil remediation. The metabolic mechanisms of these organisms aid in the transformation of environmental contaminants. Microbes adapt to a metal-polluted environment through processes of biosorption, bioaccumulation, biotransformation, and biomineralization. Remediation processes have made use of these methods. Both living and nonliving organic matter have been successfully used to purge environments of heavy metals (Olaniran et al. 2013). As the bioaccumulation approach uses living organisms and thus requires a nutrition supply and additional energy inputs, it has been established through large-scale feasibility applications of absorptive processes that dead biomass is more appropriate. Genera such as Coprinellus, Pseudomonas, Tyromyces, Gloeophyllum, Trametes, Candida, Gloeophyllum, etc., are representative of the wide variety of microorganisms utilized in bioremediation (Aliaa et al. 2016).

2.5

Dioxins as Environmental Pollutants

Figure 3 shows a dioxin, a POP that can stay in the environment and in people’s bodies for 7–11 years. Smelting, the production of various herbicides and pesticides, and chlorine bleaching of paper pulp are few examples of the industrial processes that produce dioxin uncontrolled waste from incinerators (solid waste and hospital waste). The latter are serious causes of dioxin release into the environment due to incomplete burning, yet modern technology enables incineration of waste in a way that produces minimal dioxin emissions. Certain soils and sediments, in addition to foods including dairy products, meat, fish, and shellfish, have been shown to contain extremely high levels of these compounds. Air, water, and plants all contain trace amounts. Most dioxins found in humans are from eating animals. Dioxins are dangerous substances because they are long-lasting and can be stored in fat. There are both short-term and long-term health effects associated with dioxin exposure. Implications of brief exposure include: • • • •

Liver function modifications. Disorders of pigmentation, including acne chlorosis. Improper liver functions. The neurological system, the immune system, the reproductive system, and the endocrine system can all be negatively impacted by prolonged exposure. • The effects of chronic dioxin exposure. • Many types of animal cancer have been linked to this. • There are roughly 130 known dioxins, but 2,3,7,8-tetrachlorodibenzodioxin is the most toxic one (Fig. 3). Dioxin exposure can be reduced or eliminated through source-directed efforts, such as strict regulation of industrial and residential activities to avoid the creation of dioxins (Wang et al. 2012).

Assessment of Environmental Pollutants for Their Toxicological Effects. . . Cln

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Dibenzo-1,4-dioxin Cl

Polychlorinated dibenzofuran

Cl

O

2,3,7,8-Tetrachlorodibenzodioxin Cl

O

Cl

Dioxins

Fig. 3 Dioxins as environmental pollutants

The control of human exposure to dioxins can be done through directing efforts to reduce or eliminate source production of these substances by finding alternatives to industrial activities that cause their generation.

2.6

Radioactive Environmental Pollutants

The release of radioactive substances into the environment causes radioactive contamination, which is the physical pollution of living creatures and their environment. The following are examples of activities that generate radioactive waste: • The use of nuclear weapons in warfare, such as the atomic bombs dropped by the US Air Force on the Japanese cities of Hiroshima and Nagasaki at the war’s conclusion in 1945. • Nuclear weapon testing. • The making and dismantling of nuclear weapons. • The extraction of radioactive minerals. • Radiation protection during trash disposal (medical radioactive waste features here). • Nuclear power plant accidents (e.g., the Chernobyl explosion in Ukraine in 1986 and the Fukushima nuclear disaster in Japan in 2011). Damage from nuclear accidents continues to be felt far beyond the original affected regions. Radioactive isotopes (nuclides) have two sources: natural and anthropogenic. Natural radioactive isotopes are weak emitters of radiation and are not found in abundance. On the other hand, anthropogenically produced radioisotopes are tailored strong radiation emitters that are used in energy and nuclear weapon production and in medical diagnosis and treatment. To create artificial radioisotopes, scientists attack atoms with neutrons or protons, creating unstable nuclides that, upon reaching stability, emit radiation under scientific control. One

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such process is the creation of technetium-99 m, a pure gamma emitter used in medical diagnostics (Banerjee et al. 2016).

2.7

Cosmic Rays and Other Natural Sources

Cosmic rays represent a natural source of environmental radioactive pollution. They come from the earth’s outer space and cause radioactive pollution. Cosmic rays consist of gamma ray and beta particle radiation. Almost fifteen percent of the explosive force was released as radioactive pollution. The cloud created by a nuclear explosion releases radioactive particles that can harm local water sources and the air. The release of radioactive elements into the environment causes widespread contamination after an explosion. Certain radionuclides also release alpha particles into the environment; however, due to their slow speed and short penetrating range, alpha particles are typically not regarded to be environmental contaminants. Radiation may be composed of alpha particles, beta particles, or gamma rays. Radioactive elements in the earth’s crust could potentially emit radiation that can be detected on the surface. Rocks, soil, and water contain naturally occurring radioactive elements such as Thorium-232, Potassium-40, Radon-222, Radium-224, Uranium-238, Uranium-235, and Carbon-14. Nuclear weapons and nuclear powerproducing countries are usually faced with the problem of disposing of nuclear waste. There are no chemical or biological means by which radioactivity of nuclear waste may be halted. Only through physical means can this be done. One of these physical means is burying the nuclear waste in deep inaccessible places. But there are problems. Dumping nuclear waste in oceans, for example, will certainly endanger aquatic life. This leaves deserts as the most likely places for dumping radioactive nuclear waste. However, there is the possibility that the nuclear waste may not stay hidden underground in the desert indefinitely. Access to it may happen somehow at some time, in which case danger may surface. The role of terrorist groups may be envisaged in the latter respect. Usually, nuclear energy is generated by rich politically influential countries who can use their powers to influence poor countries to help them (the rich countries) in their quest of dumping nuclear waste. In addition to running after the money, the role of corrupt regimes of the poor countries, who work against their people’s interests, may not be discounted (Liu et al. 2022).

2.8

The Chemistry of Air Pollution

Pollutants in the air that are known or suspected to cause cancer; other major health impacts, such as reproductive damage or birth defects; or adverse environmental effects are considered hazardous air pollutants. The two main types of pollutant found in the air are called “primary” and “secondary.” Both types have the potential to impede airflow and potentially prove fatal. Natural sources, such as volcanic

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eruptions and forest fires, can also contribute to air pollution, but they are less common than human-made sources like the combustion of fossil fuels like coal, oil, petrol, and gasoline. Particulate matter (PM), ammonia (NH3), and nitric acid (HNO3) are all examples of secondary pollutants, while carbon monoxide (CO), sulfur dioxide (SO2), carbon dioxide (CO2), nitrogen dioxide (NO2), nitric oxide (NO), hydrogen peroxide (H2O2), ammonium (NH4+), and volatile organic compounds (VOCs) are all examples of primary pollutants (PM). Acid rain is produced when water drops combine with sulfur dioxide or nitrogen dioxide to form sulfuric acid or nitric acid, respectively. Plants cannot survive in acidic rain conditions. These gaseous contaminants are primarily released as a result of both human activity and natural occurrences like volcanoes and forest fires. Rain that reacts with sulfur dioxide or nitrogen dioxide produces sulfuric acid and nitric acid, respectively. Plants can be killed by acid rain. All the major gaseous pollutants come not only from human industry but also from natural phenomena like volcanic eruptions and forest fires. Toxic air pollutants also include perchloroethylene, methylene chloride, dioxin, asbestos, mercury, chromium, etc. (Wang et al. 2012).

2.9

Pharmaceuticals as Environmental Pollutants

Pharmaceuticals are mainly organic compounds used to cure, mitigate, prevent, or diagnose chromium disease. When full courses of the medication are used according to instructions, the active forms of the pharmaceuticals will end up excreted mainly in the urine as metabolites or intact molecules and passed into the environment mainly in the urine. Sometimes, the pharmaceuticals may be used near its expiration date and there would be some leftovers as well. The expired and leftover drugs will be dumped in the environment at various sites in the many places where there are no regulations to control the disposal, particularly in the developing countries. Such pharmaceuticals and their metabolites can end up into the water and soil systems where they are considered as environmental pollutants. Due to their abundance, short duration of use, and low quantities in the environment, determining the health impacts of pharmaceutical pollutants and their metabolites is a challenging endeavor (Derksen et al. 2004).

2.10

Plastics as Environmental Pollutants

Plastics are polymers made out of various organic compound monomers. They stand unique because of their very high numbers and applications in today’s life. However, they are not without some drawbacks when they contaminate the environment with some leachable compounds used in their preparation and modification of properties and appearance. The leachable compounds can find their way into food consumed by humans when plastics are used as containers for storage or direct use. There are

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HO

OH O

Bisphenol A Brm

Brn

O OR

Polybrominated diphenyl ethers

OR' O Phthalates

Fig. 4 Plasticizers and fire retardants as pollutants

many leachable compounds from plastics, but three stand prominently with their frequency of presence and toxicity: bisphenol A (BPA), polybrominated diphenyl ethers (PBDE), and phthalates (Fig. 4). Due to their non-biodegradability and long persistence in the environment, plastics have been classified as persistent organic pollutants (POPs). The manufacture of polycarbonates using BPA as a comonomer accounts for 65–70% of the total BPA manufacturing. 25–30% of all BPA is used in the production of epoxy resins and vinyl ester resins. The remaining 5% is employed as both a major component and minor additive in a variety of high-performance polymers, thermal paper, and polyurethane and PVC. Bisphenol A and similar plasticizers are termed endocrine-disrupting compounds (EDCs). Once they enter the human body, plastic leachable compounds disrupt the hormonal systems. These tiny plastic pieces do great harm, given their size. Excessive exposure to phthalates can cause male infertility. The best way of fighting plastic environmental contamination is to limit the use of plastic-made items. A recent initiative of fighting environmental plastic pollution is the use of bioplastics. Bioplastics are made from biodegradable and renewable organic sources, such as food waste, cellulose, starch, etc. Nevertheless, bioplastics are not as strong as conventional plastics, but they are environmentally friendly. Hence, the responsibility falls on the shoulders of organic chemists for finding environmentally friendly alternatives either to plastics themselves or to the leachable compounds. Costeffectiveness may be a hindrance but safety should always come first (Vandenberg et al. 2007).

2.11

Polybrominated Diphenyl Ethers (PBDEs)

Polybrominated diphenyl ethers (PBDEs) are used to make a lot of fire retardants. Low fertility rates have been linked to exposure levels that are typical in homes. One of the most widespread environmental toxins is PBDEs. They are a class of

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halogenated compounds that accumulate in living organisms without degrading. As flame retardants, PBDEs can be found in a wide variety of products, including electronics, construction materials, coatings, textiles, and polyurethane foam (furniture padding). PBDEs are just as resistant to breakdown in the environment as polychlorinated biphenyls (PCBs). Fewer brominated PBDEs, such as tetra-, penta-, and hexa-PBDEs, can accumulate in the bodies of animals and humans due to their strong affinity for lipids. When compared to breast milk from Swedish women, breast milk from North American women had much higher levels of PBDEs, suggesting that exposures to PBDEs may be especially high in North America. Evidence suggests that tetra- and penta-BDEs are more dangerous and bioaccumulative than PBDEs of the octa- and deca-congener types. Common brand names for PBDE mixes include “pentabromodiphenyl ether” and “octabromodiphenyl ether.” The pentabromo product consists of almost equal parts of tetra-BDEs and penta-BDEs. Among PBDEs, pentabromo is regarded as among the most dangerous. This chemical is banned in Europe but commonly used in North America. Pentabromo is mostly produced and used in the USA. California enacted a bill in August 2003 to phase out penta- and octa-PBDEs by 2008. The toxicology of PBDEs is unknown; however, they have been linked to cancers, neurodevelopmental damage, and thyroid hormone imbalance. Like PCBs, PBDEs are neurotoxic. Minor delays in development in children have been linked to PBDE exposure. Studies on the effects of PBDEs on hormones are limited. The health impacts of this widely dispersed contaminant need to be studied further, both in the laboratory and in the field (Siddiqi et al. 2003).

2.12

Polyurethane Polymers

Polyurethane polymers (Fig. 5) are made from isocyanate monomers. They have wide industrial applications, particularly for the production of foam.

Fig. 5 Polyurethane polymer as pollutant

H N

H C

O

H

H

H

N

H O

O O

O H

Carbamate Polyurethane polymers

H

n

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3 Natural Causes of Environmental Chemical Pollution 3.1

Environmental Impacts of Volcanic Ash

Ashes from volcanoes consist of shards of rock, minerals, and molten glass. Volcanic eruptions that produce a lot of ash tend to be very dramatic. Wind plays an important role in carrying volcanic ash over long distances. Volcanic ash would fall to the ground contaminating water, sewage, and air. Rainfall helps in the process. Rainfall would wash down volcanic ash and any water-soluble gaseous or suspended material that is hanging in the air (atmosphere) to groundwater and soil, thus polluting these systems. Volcanic ash can enter any open space and when it is spread on land can be removed by the painstaking effort of shoveling usually at a considerable cost. Volcanic ash may contain the following mineral compounds: Na2O, K2O, Al2O3, Fe2O3 + FeO, FeO, MgO, CaO, Na2O, TiO2, and MnO (Cuthbertson et al. 2020).

3.2

Methane and Emission from Cattle

Scientists are trying to figure out where all the methane in the air is coming from because the concentrations keep rising. Livestock can produce methane anywhere from 250 to 500 liters each day. At this pace of production, the anticipated 2% rise in global warming due to cattle is far greater. Changing factors such as feed intake, carbohydrate type, feed processing, dietary lipid or ionophore addition, and microbiota composition all have an impact on cattle methane emissions (Jhonson and Jhonson 1995). The socioeconomic burdens of harmful chemical pollutants are considerable. Various environmental pollutants that have been discussed in this chapter were tabulated in Table 1.

4 Impact of Pollutants and Climate Change Talking about climate change, it includes changes in average temperatures and weather patterns that occur over decades or longer. Although these shifts may have a natural origin, they are likely being accelerated by human activity, particularly the combustion of fossil fuels like coal, oil, and gas (Orru et al. 2017). Greenhouse gas emissions are produced when fossil fuels are used, and these gases work like a blanket to trap the sun’s heat and raise global temperatures. Carbon dioxide and methane are the two primary greenhouse gases that are also major atmospheric pollutants. Garbage dumps are a major contributor to methane emissions, while fossil fuels provide carbon dioxide. The average global temperature has risen by 1.1 °C from the late 1800s to the present day (2023). We see all this in the news almost every day with great sorrow and we hope if something could be done about it.

Polycyclic aromatic hydrocarbons (PAHs)

Polychlorinated biphenyls (PCBs)

Fluorocarbons and chlorofluorocarbons

Heavy metals

2.

3.

4.

5.

S. no. 1.

Name of environmental pollutants Environmental chemical pollutants (ECPs)

Biphenyl-catabolic enzymes in bacteria can cometabolize a wide variety of PCB congeners Degrade chlorinated compounds, can be coaxed to degrade fluorinated compounds as well Biotransformation and mineralization by bacterial enzymes Achromobacter strains, Rhodococcus globerulus

Skin infections, mutagenesis

Gordonia sp., Dehalococcoides bacteria Pseudomonas, Alcaligenes, Sphingomonas, Rhodococcus, and Mycobacterium

Cancer

Cancer, hepatotoxicity

Trichlorofluoromethane, CFCl3 (CFC-11)

Aluminum (Al), antinomy (Sb), barium (Ba), beryllium (Be), bismuth (Bi), cadmium (Cd), gallium (Ga), germanium (Ge), gold (Au), indium (In), lithium (Li), nickel (Ni), platinum (Pt), silver (Ag), strontium (Sr), tellurium (Te), thallium (Tl), tin (Sn), titanium (Ti), vanadium (V), and uranium (U)

(continued)

Furukawa et al. (2000)

Naphthalene degradation

Xanthomonas sp.

Cataracts, kidney and liver damage, and jaundice

Benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(g,h,i) perylene, and indeno(1,2,3cd)pyrene Polychlorinated dibenzofurans, polychlorinated dibenzo-p-dioxins

References RiosHernandez et al. (2003) Peng et al. (2008)

Mechanism of action Decarboxylation techniques

Societal hazards Nausea, vaginal bleeding, fatigue

Examples Polychlorinated biphenyl, tributyltins

Microbial degradation of pollutants CytophagaFlexibacterBacteroides group

Table 1 A list of environmental pollutants, their societal impacts, microbial degradation pathways, and mechanism of action

Assessment of Environmental Pollutants for Their Toxicological Effects. . . 81

Radioactive pollutants

Pharmaceutical pollutants

7.

8.

S. no. 6.

Name of environmental pollutants Dioxins

Table 1 (continued)

Radioactive dust and nuclear dust, U-235, U-238, Np-237, Cs-137, Pu-239, Am-241, Tc-99, and Sr-90 Chemicals

Examples Dibenzo 1,4-dioxin, polychlorinated dibenzo-pdioxins (PCDD), and polychlorinated dibenzofurans (PCDF)

Allergic reactions, hypersensitive reactions

Cancers

Societal hazards Elevated risks of cancerrelated mortality, prenatal abnormalities, cough, and paresthesia

Pseudobacter, Arthrobacter, Enterobacter

Geobacter sp.

Microbial degradation of pollutants Dehalococcoides Mechanism of action Special angular dioxygenases often begin the degradation process by attacking the ring next to the ether oxygen. White-rot fungus, which uses extracellular lignin-degrading peroxidase, can also cometabolically attack chlorinated dioxins in aerobic conditions Conversion of oxidized soluble radionuclides to reduced and insoluble radionuclides As food, the microbes utilize these sources and degrade

Shukla et al. (2017)

References Field and SierraAlvarez (2008)

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According to environmental experts, it is the duty of every person on the planet to slow down or stop the progression of global warming and climate change. International environment organizations, the United Nations, and the governments of the individual member states should make and coordinate the most significant and leading efforts. In order to minimize this climatic change due to environmental pollution, expanding the greenery landscape is one of the best measures men can implement, as plants take in carbon dioxide from the environment and give off oxygen. According to UN estimates, the replacement of fossil fuel with renewable energy sources needs about $4.3 trillion. In today’s prices, this amount is affordable upon contribution by all UN member states with the highest contributions falling on the shoulders of the industrialized rich countries (Pilli et al. 2021).

5 Conclusions and Recommendations How quickly ecosystems are being destroyed by pollution is quite concerning. It is important to examine global public health issues like greenhouse gas emissions, water pollution, and improper waste management from multiple angles, such as social, economic, legislative, and environmental engineering systems, as well as the role that healthy lifestyle choices play in fortifying these infrastructures and preventing further epidemics. Environmental pollution and contaminants have disastrous biological effects on organisms, including cancer, oxidative stress, cardiovascular disease, erectile dysfunction, and neurotoxicity. Environmental pollution has been blamed by a large number of studies as the leading cause of death and illness. Therefore, it is time to take action and control pollution, which is possible by creating awareness among the population by providing some study materials focusing on recent development on environmental pollutants and pollution. Whatever humans do, the environment will always contain chemical pollutants, harmful to human health or otherwise. In order to curtail or remove the harmful effects of chemical pollutants, planning is necessary: how the chemicals are made, what are the materials used in their manufacture, how they are stored, how they are applied for specific purposes, and how they are disposed of or kept at bay. They may lead to population displacements, which are associated with economic problems. In addition, curtailing or removal of the chemicals from the environment is costly. Furthermore, the diseases the chemicals cause need to be treated at high cost.

References Aliaa ME-B, Eltayeb KM, Mostafa AR, El-Assar SA (2016) Biodegradation of industrial oil-polluted wastewater in Egypt by bacterial consortium immobilized in different types of carriers. Pol J Environ Stud 25:1901–1909 Azevedo LF, Karpova N, Rocha BA, Barbosa Junior F, Gobe GC, Hornos Carneiro MF (2023) Evidence on neurotoxicity after intrauterine and childhood exposure to organomercurials. Int J Environ Res Public Health 20:1070–1089

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Balzano S, Sardo A, Blasio M, Chahine TB, Dell’Anno F, Sansone C, Brunet C (2020) Microalgal metallothioneins and phytochelatins and their potential use in bioremediation. Front Microbiol 11:517–525 Banerjee D, Kim D, Schweiger MJ, Kruger AA, Thallapally PK (2016) Removal of TcO4(-) ions from solution: materials and future outlook. Chem Soc Rev 45:2724–2739 Barbosa F Jr, Rocha BA, Souza MCO, Bocato MZ, Azevedo LF, Adeyemi JA, Santana A, Campiglia AD (2023) Polycyclic aromatic hydrocarbons (PAHs): updated aspects of their determination, kinetics in the human body, and toxicity. J Toxicol Environ Health B Crit Rev 26(1):28–65 Bensefa-Colas L, Andujar P, Descatha A (2011) Intoxication par le mercure [Mercury poisoning]. Rev Med Interne 32:416–424 Bhadouria R, Das S, Kumar A, Singh R, Singh VK (2020) Mycoremediation of agrochemicals. In: Agrochemicals detection, treatment and remediation. Elsevier, Butterworth-Heinemann, pp 593–620 Briffa J, Sinagra E, Blundell R (2020) Heavy metal pollution in the environment and their toxicological effects on humans. Heliyon 9:e04691–e04699 Carpenter DO (2006) Polychlorinated biphenyls (PCBs): routes of exposure and effects on human health. Rev Environ Health 21:1–23 Chormare R, Kumar MA (2022) Environmental health and risk assessment metrics with special mention to biotransfer, bioaccumulation and biomagnification of environmental pollutants. Chemosphere 302:134836–134845 Cuthbertson J, Stewart C, Lyon A, Burns P, Telepo T (2020) Health impacts of volcanic activity in Oceania. Prehosp Disaster Med 35:574–578 Derksen JG, Rijs GB, Jongbloed RH (2004) Diffuse pollution of surface water by pharmaceutical products. Water Sci Technol 49:213–221 Dixit R, Malaviya D, Pandiyan K, Singh UB, Sahu A, Shukla R, Singh BP, Rai JP, Sharma PK, Lade H (2015) Bioremediation of heavy metals from soil and aquatic environment: an overview of principles and criteria of fundamental processes. Sustainability 7:2189–2112 Field JA, Sierra-Alvarez R (2008) Microbial degradation of chlorinated dioxins. Chemosphere 71: 1005–1018 Filippi L, Pini A, Cammalleri M, Bagnoli P, Dal Monte M (2022) β3-Adrenoceptor, a novel player in the round-trip from neonatal diseases to cancer: suggestive clues from embryo. Med Res Rev 42:1179–1101 Furukawa K (2000) Biochemical and genetic bases of microbial degradation of polychlorinated biphenyls (PCBs). J Gen Appl Microbiol 46:283–296 He QL, Zhang L, Liu SZ (2021) Effects of polychlorinated biphenyls on animal reproductive systems and epigenetic modifications. Bull Environ Contam Toxicol 107:398–405 Hong YS, Kim YM, Lee KE (2012) Methylmercury exposure and health effects. J Prev Med Public Health 45:353–363 Johnson KA, Johnson DE (1995) Methane emissions from cattle. J Anim Sci 73:2483–2492 Liu C, Benotto M, Ungar K, Chen J (2022) Environmental monitoring and external exposure to natural radiation in Canada. J Environ Radioact 243:106811–106815 Lodeiro C, Capelo-Martínez JL, Santos HM, Oliveira E (2021) Impacts of environmental issues on health and well-being: a global pollution challenge. Environ Sci Pollut Res Int 28:18309–18313 Manisalidis I, Stavropoulou E, Stavropoulos A, Bezirtzoglou E (2020) Environmental and health impacts of air pollution: a review. Public Health Front 8:1–13 Mojiri A, Zhou JL, Akiyoshi Ohashi A, Ozaki N, Kindaichi T (2019) Comprehensive review of polycyclic aromatic hydrocarbons in water sources, their effects and treatments. Rev Sci Total Environ 696:133971–133980 Olaniran AO, Balgobind A, Pillay B (2013) Bioavailability of heavy metals in soil: impact on microbial biodegradation of organic compounds and possible improvement strategies. Int J Mol Sci 14:10197–10128

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Orru H, Ebi KL, Forsberg B (2017) The interplay of climate change and air pollution on health. Curr Environ Health Rep 4:504–513 Peng RH, Xiong AS, Xue Y, Fu XY, Gao F, Zhao W, Tian YS, Yao QH (2008) Microbial biodegradation of polyaromatic hydrocarbons. FEMS Microbiol Rev 32:927–955 Pilli S, Pandey AK, Pandey V, Pandey K, Muddam T, Thirunagari BK, Thota ST, Varjani S, Tyagi RD (2021) Detection and removal of poly and perfluoroalkyl polluting substances for sustainable environment. J Environ Manag 297:113336–113342 Rahman Z, Singh VP (2019) The relative impact of toxic heavy metals (THMs) (arsenic (As), cadmium (Cd), chromium (Cr)(VI), mercury (Hg), and lead (Pb)) on the total environment: an overview. Environ Monit Assess 191:419–440 Rios-Hernandez LA, Gieg LM, Suflita JM (2003) Biodegradation of an alicyclic hydrocarbon by a sulfate-reducing enrichment from a gas condensate-contaminated aquifer. Appl Environ Microbiol 69:434–443 Saleha Banu B, Danadevi K, Jamil K, Ahuja YR, Visweswara Rao K, Ishap M (2001) In vivo genotoxic effect of arsenic trioxide in mice using comet assay. Toxicology 162:171–177 Shukla A, Parmar P, Saraf M (2017) Radiation, radionuclides and bacteria: an in-perspective review. J Environ Radioact 180:27–35 Siddiqi MA, Laessig RH, Reed KD (2003) Polybrominated diphenyl ethers (PBDEs): new pollutants-old diseases. Clin Med Res 1:281–290 Singh P, Singh R, Singh VK, Bhadouria R (2021) Pollutants and water management: resources, strategies and scarcity. Wiley, pp 45–56 Sutton DJ, Tchounwou PB (2007) Mercury induces the externalization of phosphatidylserine in human proximal tubule (HK-2) cells. Int J Environ Res Public Health 4:138–144 Tchounwou PB, Yedjou CG, Dorsey WC (2003) Arsenic trioxide-induced transcriptional activation and expression of stress genes in human liver carcinoma cells (HepG2). Cell Mol Biol 49:1071– 1079 Tchounwou PB, Yedjou CG, Patlolla AK, Sutton DJ (2012) Heavy metals toxicity and the environment. EXS 101:133–164 Tian Y, Li Y, Sun S, Dong Y, Tian Z, Zhan L, Wang X (2023) Effects of urban particulate matter on the quality of erythrocytes. Chemosphere 13:137560–137570 Tripathi S, Singh VK, Srivastava P, Singh R, Devi RS, Kumar A, Bhadouria R (2020) Phytoremediation of organic pollutants: current status and future directions. Abatement of environmental pollutants. Elsevier, pp 81–105 Vandenberg LN, Hauser R, Marcus M, Olea N, Welshons WV (2007) Human exposure to bisphenol A (BPA). Reprod Toxicol 24:139–177 Wang X, Ni Y, Zhang H, Zhang X, Chen J (2012) Formation and emission of PCDD/Fs in Chinese non-wood pulp and paper mills. Environ Sci Technol 46:12234–12240 Wang Z, Walker GW, Muir DCG, Nagatani-Yoshida K (2020) Toward a global understanding of chemical pollution: a first comprehensive analysis of national and regional chemical inventories. Environ Sci Technol 54:2575–2582 Yilmaz N, Vigil FM, Donaldson B (2022) Fuel effects on PAH formation, toxicity and regulated pollutants: detailed comparison of biodiesel blends with propanol, butanol and pentanol. Sci Total Environ 25:157839–157851

Organic Micropollutants and Their Effects on the Environment and Human Health Archna Kumar, Deepika, Dhruv Tyagi, Tarkeshwar, and Kapinder

Abstract The rapid increase in the urbanization process across the world leads to the production of micropollutants (MPs) that adversely impact the environment and threaten our health. These micropollutants based on their natural properties are categorized as organic micropollutants (OMPs) such as organochlorine pesticides, hormones, polyaromatic hydrocarbons, etc. and inorganic micropollutants including heavy metals. The chemicals used in various agricultural practices, industries, medical fields, power generation, and water treatment are few among key polluters. These MPs are highly toxic, persistent, and nondegradable, which slowly accumulate in living organisms and also exhibit the potential to transport over longer distance through the environment. MPs influence human health mainly by eliciting various dysfunctions like neurodevelopmental defects in children, thyroid disorders, bone defects, and endocrine-related malignancy. These pollutants also degrade soil health and its associated microbes, various biogeochemical processes associated with soil ecology, and genetic alteration in microbes. The fate, incidence, and eco-toxicological effect of MPs in the environment are a rather new challenge countenance by human societies. The emancipation of these MPs in the absence of any regulatory procedure leads to cause major environmental concerns even at their very low concentrations. The consequences of these MPs in the environment are not necessarily due to their persistence; however, it exists due to their active biological nature collectively with their continuous emission, which makes them emerging pollutant. This chapter includes the types of micropollutants, their sources, pathways, fate, distribution, and possible remediation of MPs in the environment. The future perspective is to develop eco-friendly and cost-efficient methods for the

A. Kumar · Deepika · D. Tyagi Amity Institute of Biotechnology, Amity University, Noida, UP, India e-mail: [email protected] Tarkeshwar Department of Zoology, Kalindi College, University of Delhi, Delhi, India e-mail: [email protected] Kapinder (✉) Department of Zoology, University of Allahabad, Prayagraj, UP, India © The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 R. Bhadouria et al. (eds.), Organic Micropollutants in Aquatic and Terrestrial Environments, https://doi.org/10.1007/978-3-031-48977-8_5

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identification and fate of various micropollutants and their metabolites as well as various policies to reduce their concentration in the environment. Keywords Eco-toxicological effect · Environment · Human health · Micropollutants

1 Introduction Industrialization and urbanization have led to a notable rise in the standards of living for a major section of the world’s population since the nineteenth century. It has allowed societies to transition from prioritizing the collective to prioritizing the individual. Thus, the quality of life of those individuals has continued to improve. However, this sudden elevation of the industry also has detrimental effects on the environment and the material output of the human species in terms of the quantity of waste generated (Ngwepe and Aigbavboa 2015). The amount of waste generated in most developed and developing countries has continued to rise in the past 200 years due to industrial practices, consumer habits, and the increase in urbanization (Maalouf and Agamuthu 2023). While the sheer quantity of increased waste can be seen as an inevitable consequence of consumption, the new types of waste, which have contaminated the ecosystem, are a matter of concern. Organic micropollutants (OMPs) are small organic compounds, typically found at low concentrations in the environment, which can have adverse effects on ecosystems, wildlife, and human health due to their persistence, bioaccumulation potential, and toxicity. These compounds are often anthropogenic, originating from various sources such as industrial, agricultural, and domestic activities, and can be found in water, air, soil, and sediments (Fig. 1). This category of pollutants has seen a spike in concentration in the environment as it is almost completely produced by modern innovations in sectors such as agriculture, waste and water treatment, medicine, and manufacturing). There are many categories of organic micropollutants which are primarily classified based on their origins such as industrial chemicals, disinfection by-products (DBPs) from wastewater treatment, pesticides from agriculture, waste from personal care products, and metabolism-affecting chemicals in the pharmaceutical industry. The range of chemicals that are considered to be OMPs is vast due to the various effects, each of these substances can have one component of the ecosystem as well as human and animal health. Some of these chemicals are organochlorine, organophosphate and triazine pesticides, hormones, polyacrylamide hydrocarbons (PAMs), DBPs, antibiotics, endocrine-disrupting chemicals (EDCs), and organic compounds containing heavy metals. The common factor that encompasses these substances is their relatively small concentration present within the environment which has disastrous effects on the ecosystem as a whole. They display effects on reproductive health, the endocrine system, enzyme interactions, and neurological functions and can induce disorders related to them. These have been observed and verified in studies conducted on humans and a plethora of animals. Children, pregnant women,

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Animals

Agriculture OMPs

Fig. 1 The cycling of organic micropollutants (OMPs) in the ecosystem

and medically compromised individuals are especially prone to the negative effects of these chemicals. They also display toxicity toward living organisms in the ecosystems they contaminated and can severely affect the aquatic and terrestrial biodiversity of the region. Microbial organisms are similarly affected by these pollutants as they can interfere with biogeochemical processes involving microorganisms and induce mutations in naturally occurring microbes and disrupt the composition of organisms in a region. This has detrimental effects on soil health (as the soil is frequently exposed to OMPs by the application of pesticides) and the water quality of the ecosystem (Tripathi et al. 2020a, b). Organic micropollutants are relatively new occurrences in the environment in the history of this planet. They are a result of modern human activities and thus their effects on the ecosystem as a whole are disruptive to the natural ecology and food chain. The management of this new challenge is a monumental task due to the lack of viable alternatives for most of the products that produce OMPs in the global market. This area of legislation is also severely lacking in regulation, in order to promote the affordability and operational feasibility of private industries. However, the biological activity of this class of micropollutants makes them a major threat to the balance in the ecosystem as well as to human and animal health. This chapter elaborates upon the sources of these OMPs, their impact on health and the ecosystem, their pathways into the ecosystem, and possible methods of remediation of these chemicals.

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2 Sources of Organic Micropollutants 2.1

Agricultural and Pesticides

The primary pollutants released by farm activities are pesticides and other chemicals used to treat weeds, fungi, insects, and other pests. Pesticides such as organochlorines, carbamates, organophosphates, triazines, and synthetic pyrethroids enter the environment by runoffs into lakes, rivers, and canals (Stuart et al. 2012; Bhadouria et al. 2019; Tripathi et al. 2020a, b). Researchers have found prominently used pesticides such as DDT (dichlorodiphenyltrichloroethane), heptachlor, and atrazine in significant concentrations in the groundwater even years after they were discontinued. They also detected the presence of 53 other pesticide metabolites in drinking water based on the usage of parent compounds, persistence, and mobility (Sinclair et al. 2010). Most major pesticide metabolites that have been in use have been proven to have toxic effects on aquatic and terrestrial life, leading to a reduction in biodiversity (Isenring 2010). They have also been shown to have causative agents of reproductive (Bapayeva et al. 2017), endocrinal (Leemans et al. 2019), and neurological diseases (Sabarwal et al. 2018) in humans. Cases in groundwater contamination have also been witnessed which demonstrate that pesticide metabolites have been detected at a higher presence than that of the original parent compound itself (Kolpin et al. 2004; Lapworth and Gooddy 2006). A popular organophosphate herbicide known as glyphosate degrades to form aminomethylphosphonic acid (AMPA) as a pesticide’s metabolite. Both these compounds are highly water soluble. The accumulation of AMPA has been associated with moderate toxic effects on aquatic creatures and affects their biodiversity (Levine et al. 2015). A study by Kolpin et al. (2006) found that the concentration of AMPA in surface water was nearly four times than that off the concentration of glyphosate in the same water (Table 1).

2.2

Pharmaceuticals

Pharmaceuticals and pharmaceutical derivatives are one of the most significant sources of micropollutants in the environment, as the chemicals involved are specifically intended to be biologically active and have a direct effect on the metabolic activities of humans and animals. They pass through the body with minimal or no changes or modifications to their molecular structure as they travel as conjugates (Sarmah et al. 2006; Kümmerer 2009). Thus, they eventually become part of the wastewater generated by the organisms that consume and excrete it and end up in rivers, lakes, canals, water treatment facilities, and even irrigation water (Daughton and Ternes 1999). The primary sources of pharmaceutical pollution are drugs, EDCs, personal care products, painkillers, hormones, and antibiotics (Vatovec et al. 2021).

Member Organochlorines, carbamates, organophosphate, triazines and synthetic pyrethroids, and aminomethylphosphonic acid (AMPA)

Drugs, EDCs, personal care products, painkillers, hormones, and antibiotics

Perfluorochemicals (PFCs) and benzotriazole

Type Agricultural pesticides

Pharmaceuticals

Industrial processes

Abundance Groundwater and drinking water

Wastewater, rivers, lakes canals, water treatment facilities, and irrigation water

They are found even in remote water bodies like deep sea

Source From agricultural fields and areas with intensive farming activities

Human and animal waste Hospital waste and unused medical equipment and drugs

They are converted from chemicals like phthalates, adipates, resins, chlorinated solvents, methyl tert-butyl, and bisphenols

Table 1 Sources of organic micropollutants (OMPs) in the environment

Affects the aquatic life in the deep sea Contamination of water bodies

Affects the metabolic activity of animals and humans

Harmful effects on flora, fauna, and environment 1. Causes reproductive endocrinal and neurological diseases in humans 2. Contamination in the groundwater 3. AMPA shows moderate toxicity toward aquatic animals

(continued)

References Stuart et al. (2012), Tripathi et al. (2020a, b), Bhadouria et al. (2019) Bapayeva et al. (2017) Leemans et al. (2019) Sabarwal et al. (2018) Kolpin et al. (2004), Lapworth and Gooddy (2006) Vatovec et al. (2021) Sarmah et al. (2006), Kümmerer (2009) Daughton and Ternes (1999) Arslan et al. (2017) Arslan et al. (2017) Moran et al. (2005)

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Type Water treatment

Member Trihalomethanes and haloacetic acids

Table 1 (continued) Source Disinfectants and chemicals like ozone, chlorine, chloramine, and chlorine dioxide used to treat pathogens that cause infectious diseases

Abundance They get evaporated along with water and by rainstorm, they get resumption in the soil

Harmful effects on flora, fauna, and environment Degradation of the soil quality and contamination in water bodies and rainwater that further leads to acid rains References Pavelic et al. (2005, 2006) Barber et al. (1997) Ates et al. (2007)

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Over the years, pharmaceutical micropollutants have been detected in urban water bodies and wastewater, due to the deposition of human and animal waste which contains various pharmaceutical products (Arslan et al. 2017). Hospital waste and the improper disposal of unused medical equipment and drugs have also been notable sources of this category of micropollutants. Sewage treatment facilities and wastewater treatment plants are incapable of removing a significant amount of these pollutants from the water as they are usually ignored during secondary and tertiary treatment, and thus, most of the pollutants pass through these checkpoints into the water sources and eventually into food chains (Lishman et al. 2006; Santos et al. 2007). As a result, more than 4000 of the drugs ever used for human and animal treatment have been detected in the environment over the years (Scudellari 2015) (Table 1).

2.3

Industrial Processes

Industrial processes utilize various chemicals in practices such as carpeting, textiles, paper wrapping, electroplating, plastics, foam manufacturing, etc., which when released into the environment, are capable of acting as major organic micropollutants in the ecosystem. Even before degradation, some of these chemicals are classified as major pollutants such as phthalates, adipates, resins, chlorinated solvents (Arslan et al. 2017), methyl tert-butyl, and bisphenols (Moran et al. 2005), but after conversion to metabolites, they display more toxicity in the environment, like perfluorochemicals (PFCs) and benzotriazole. While the actual concentration of these chemicals in the environment is reportedly low, the primary concern for these chemicals is their natural resistance to degradation. Chemicals like PFCs tend to stay in water bodies in their undegraded forms and can thus be even found in remote regions like the deep sea, where they can affect aquatic life. PFCs which possess a relatively volatile nature are capable of undergoing transformation into sulfonates and carboxylic acids which are highly persistent in the environment (La Farré et al. 2008). Discharge forms the manufacturing industries of pesticides, and pharmaceuticals also contribute to organic micropollutants and contaminations in the environment.

2.4

Water Treatment

The polluting chemicals and substances used for sanitation and other cleansing treatments are also considered another category of organic micropollutants. This includes examples like disinfectants and chemicals like ozone, chlorine, chloramines, and chlorine dioxide which are used in the treatment of water to control pathogens and infectious diseases. They react with the organic components that

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constitute the water and form disinfection by-products (DBPs) which act as micropollutants in the environment. Some commonly observed metabolized micropollutants in DBP masses are trihalomethanes and haloacetic acids, which are derivatives of halogens and halogenic compounds used in sanitation. The presence of the compounds is variable based on the type and degree of pollutant as well as the treatment provided to the DBP masses before their dispersion into bodies of water (Pavelic et al. 2005, 2006). Some DBPs are prone to volatilization, degradation, and sorption during wetland treatment (Barber et al. 1997). Other water treatment processes like chlorination can cause the formation of DBPs like trihalomethanes during rainstorms, resuspension of sediments, and land surface runoffs (Ates et al. 2007).

3 Impact of Organic Micropollutants 3.1

Impact of Organic Micropollutants on the Biotic Component of the Ecosystem

3.1.1 3.1.1.1

Humans Impact of Pesticides

Micropollutants produced in the agricultural industry have significant health effects on humans and animals due to their toxicity as well as properties that induce various disorders. Pesticides, which are the primary organic micropollutants produced by this sector, have been researched, regulated, and restricted based on decades of studies and evidence that links them to carcinogenicity, teratogenicity, mutagenicity, endocrine-related disorders, reproductive disorders, and neurological disorders (Nicolopoulou-Stamati et al. 2016). They are also characterized by their tenacious persistence in the environment which leads to their effects being experienced despite their discontinuation. The toxicity of pesticides in living organisms is well documented, as it has been observed that pesticides are toxic for all organisms above certain concentrations. Cases related to occupational, incidental, and consumption-based pesticide toxicity have led to hospitalizations and even death (Nicolopoulou-Stamati et al. 2016). Classes of pesticides known as neonicotinoids have been identified as chemicals that play a role in certain disorders of the central nervous system, such as Alzheimer’s disease, schizophrenia, depression, and Parkinson’s disease (Hashimi et al. 2020). Another class known as pyrethroids has been reported to damage DNA in human sperm cells and lead to disorders in the reproductive system of humans. They have also been associated with issues in the central nervous system, endocrine disorders, and even cancer. Researchers have also linked pyrethroids to hyperexcitation, aggressiveness, incoordination, tremors, and seizures (Sarwar 2015). Pesticides from the carbamate category have been known to increase the risk of

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dementia in affected individuals, cause neurobehavioral disorders, and are potential causative agents for non-Hodgkin’s lymphoma (Wahab et al. 2016).

3.1.1.2

Pharmaceuticals

Organic micropollutants that have their origins in the pharmaceutical industry are especially dangerous and effective against humans due to them being the target demographic for the action of the chemical products involved. They have been associated with endocrinal disruption, cancer, and developmental disorders in humans. The enzymatic effects due to endocrinal disruptions caused by pharmaceutical micropollutants have been linked to a multitude of conditions in affected individuals. Micropollutants such as estrogen, androgen, and progesterone are capable of causing problems with fertility and breast cancer as well as reproductive disorders (Daughton and Ternes 1999). Endocrine-disrupting chemicals (EDCs) have been associated with androgenic and estrogenic effects and have even been linked to cancer progression, due to some of their effects observed on tumor microenvironments (Buoso et al. 2020).

3.1.1.3

Disinfection By-Products (DBPs)

Research on the effects of chlorination and other forms of water treatment has discovered that disinfection by-products (DBPs) like trihalomethane have links to disorders ranging from endocrine disruption to pregnancy complications (Plewa and Wagner 2015). Haloacetic acids have also been demonstrated to display severe toxicity to humans. Iodoacetic acid, in particular, is stated to be the most genotoxic DBP to have been researched as of 2019, while iodoacetamide and diiodoacetamide are the most cytotoxic (Dong et al. 2019).

3.1.2 3.1.2.1

Biodiversity Aquatic

The pathways that are prevalent for the dispersion of micropollutants rely heavily on water bodies and the consumption of the water in those bodies. This is due to the fact that most sources of organic micropollutants involve disposal or contact with water. Human and animal body waste containing pharmaceutical micropollutants is mostly disposed of in water bodies, and pesticide runoffs from soil enter rivers, lakes, and groundwater (Mahmood et al. 2016). Industrial waste is also disposed of in bodies of water, and water treatment is performed on water bodies themselves. This makes them specifically prone to this type of pollution and puts the ecosystem and the organisms that inhabit this habitat in elevated danger as compared to terrestrial organisms.

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Studies have shown that herbicide content in water bodies drastically reduces the quantity of dissolved oxygen in them, leading to a reduction in the fish population as well as general biodiversity in these water bodies (Helfrich et al. 2009). Other pesticides like malathion have reduced the quantity of plankton and periphyton in water, which in turn affects the tadpole hatching rate in affected regions (Relyea and Hoverman 2008). These effects compile to have direct significant effects on the organisms that are prone to the toxicity of these chemicals while also indirectly affecting the organisms which are present in the food chains that contain these affected organisms. Researchers also demonstrated the negative effects of phthalates on planktonic species like Daphnia magna above a certain concentration in water (Seyoum and Pradhan, 2019). The endocrine-disrupting effect of phthalate esters was also determined in studies conducted on their negative effects in the surface water of China (Sun et al. 2021). Sublethal di-n-butyl phthalate was also shown to be genotoxic toward fish species such as Oreochromis niloticus, in controlled laboratory conditions (Karasu Benli et al. 2016).

3.1.2.2

Terrestrial

Amphibians, fish-eating birds, small mammals, and bees have experienced the most impact of organic micropollutants (Carvalho 2017). Unlike aquatic organisms, where micropollutants are introduced to the populations through the medium of water, terrestrial animals are exposed to micropollutants mostly through the food chain. Thus, pesticides are the primary micropollutants that affect living organisms on land, due to their persistence and ability to deposit into fat tissue. This allows them to travel up the food chain and affect all the organisms within that food chain. It has been considered that the decrease in the population of arctic seals can be linked to pesticide and chlorinated hydrocarbon accumulation in the food chain. These micropollutants have an adverse effect on the immune system of animals, thereby increasing mortality rates to infections. Striped dolphins, beluga whales, and sea lions are also speculated to be affected by similar forms of accumulation of toxic micropollutants (Cunningham and Cunningham 2004). Terrestrial organisms can also be exposed to non-pesticide OMPs through the various contaminated water sources in their ecosystem. This exposes them to a range of OMPs, from pharmaceutical micropollutants to industrial chemicals. Pesticide OMPs have also been linked to reproductive disorders in animal populations ranging from issues like reproductive toxicity to delayed sexual maturation of animals. Atrazine is a chemical from a class of pesticides known as triazines, which has been linked to such negative effects (Nicolopoulou-Stamati et al. 2016). The organic micropollutants known as polychlorinated biphenyls (PCBs) are highly toxic to organisms and were used in industrial practices as well as agriculture throughout the twentieth century. They were banned in 2001 across the world based on research proving their toxicity and degree of harm to the ecosystem. However, it has still been detected in fish, birds, and other animals and has the potential to reduce the population of these organisms (Pesiakova et al. 2018).

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Impact of Organic Micropollutants on the Abiotic Component of the Ecosystem Soil Health

Soil health is mostly affected by pesticides and similar classes of organic micropollutants such as herbicides and fungicides. Decades of research have discovered many examples of the negative effects of these chemicals on the fertility of soil as well as its quality. Buprofezin is known to be a causative agent for adverse effects to invertase in soil. It affects the enzymatic activity of microorganisms present, thus altering the metabolic functions of the necessary microbes in the soil. Enzymatic activity is observed to decline after three applications of the chemical in the soil (Maddela and Venkateswarlu 2018). A report on a study on chlorophenols indicated that composts treated with pentachlorophenol (PCP) resulted in the inhibition of microbe growth within the target soil (El-Naas et al. 2017). The usage of pesticides, whether combined or separate, results in the reduction in the concentration of microbial diversity in the soil, or an alteration in the community of microbes itself (Muturi et al. 2017). Pesticides are usually implemented as targeted toward specific pests or negative actors; however, they can have indiscriminate effects on the organisms that are important in regulating and maintaining soil health (Yousaf et al. 2013). This can adversely affect the nutrient cycle and retention, leading to poor soil quality and reduced soil fertility.

3.2.2

Water

The proliferation of micropollutants such as pharmaceutical products, pesticides, and DBPs in water sources can have major negative effects on the flora and fauna of the affected water bodies. The biodiversity within these ecosystems has been altered over years of exposure, such as in the case of the studies done on the ecotoxicological effects on phytoplankton which were exposed to DBPs (Cui et al. 2022). The consumption of these affected water bodies can also be detrimental to the health of the populations which use these water bodies as a water source. Most micropollutants end up in the aquatic ecosystem as water serves as the primary medium for OMPs in the environment. While OMPs are also found in the soil and in vapor phases, contamination through water sources is the most common method of exposure.

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4 Pathways of Organic Micropollutants 4.1

Soil

A major source of soil contamination associated with organic micropollutants is various pesticides used in the agricultural industry to control pests, weeds, and other organisms that hinder crop growth and agricultural yield (Wołejko et al. 2020). While the application of pesticides such as insecticides, fungicides, and herbicides leads to toxic effects on the terrestrial biodiversity of the region while also negatively affecting soil health, another major consequence of this practice is also the proliferation and distribution of these OMPs into other sectors of the environment (Mahmood et al. 2016). Pesticide runoffs from farming areas can significantly increase the impact of the chemicals used as pesticides on the local and extended ecosystem. This is assessed using the runoff potential of water streams that leave farmland and aggregate into larger water bodies (Schriever and Liess 2007). Studies conducted in Lagos on the bioaccumulation of toxic OMPs showed how micropollutant (organochlorines, polychlorinated biphenyls) runoffs and leaching led to further contamination of soil and water in the area and beyond (Alani et al. 2013). OMPs from pesticides can also end the food chain through the soil and enter living organisms. This negatively impacts the biodiversity of the animals involved in the food chain and can destabilize the ecosystem. Organophosphates have been studied to enter the food chain and affect the health of the animals within it (Rezg et al. 2010).

4.2

Water

Water is the primary means of exposure and distribution of organic micropollutants into the environment, as nearly all OMP-producing sources have the end point of their pollutants in water bodies. Water receives pesticide runoff from the soil due to streams which combine into larger rivers. Portions of the water cycle act as extremely effective means of transportation of micropollutants between the source and the affected subjects (Yang et al. 2023). Pharmaceutical micropollutants are only found in this medium, as human waste disposals such as urine, personal care products, and excrement are disposed of in water bodies. These waste sources contain pharmaceutical micropollutants which then enter the ecosystem and lead to the exposure of organisms to them. Research conducted on drinking water in the United States found the presence of pharmaceutical micropollutants in more than 80% of the country’s drinking water (Kolpin et al. 2002). This represents a dangerously large metric in terms of exposure, as it verified that a significant majority of the country’s population has been continuously exposed to these chemicals. Water samples from Europe, Africa, and Asia have also been analyzed, with results concluding the presence of pharmaceutical micropollutants in

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them (Benotti et al. 2009). Long-term exposure to these micropollutants through skin and inhalation can have serious effects on the health of the populations exposed to them (Fatta-Kassinos et al. 2011). Water bodies such as streams, rivers, and lakes also serve as water sources for terrestrial animals which are thus also exposed to OMPs. This allows the OMPs to enter the food chain and affect even more carnivorous and omnivorous animals. Industrial wastes, disinfection by-products, and pharmaceutical wastes can further affect aquatic biodiversity in these water bodies due to their toxicity to living organisms as well as their metabolism-disrupting and endocrine-disrupting properties. Thus, water serves as the most impactful distributor of micropollutants in the entire ecosystem.

4.3

Air

Air also serves as a medium of exposure to organic micropollutants; however, it has a smaller share of cases of exposure and primarily serves as a transmission medium of moving OMPs from their sources to water bodies which serve as the main medium of exposure. OMPs volatilize into the air upon being exposed to it and remain in the atmosphere, where they can be inhaled leading to exposure. However, most of these pollutants have a small concentration and eventually are brought down to the surface by rainfall. Rainwater condenses and collects aerial OMPs by dissolution and carries them to the earth. This water then eventually aggregates into streams and rivers, and thus the pathways of exposure of OMPs through water are sustained. Studies on this phenomenon have confirmed the presence of OMPs such as polycyclic aromatic hydrocarbons (PAHs), phthalate ester (PEs), pesticides, and polychlorinated biphenyls (PCBs) in rainwater (Guidotti et al. 2000). Another study conducted in the snow in Norway also concluded the presence of PAHs, phthalic acid esters, fatty acid ethyl esters, and alkanes (Shubhankar and Ambade 2016).

4.4

Food Chain

The various food chains in their respective ecosystems form the final branch of transmission for organic micropollutants for many organisms. Both aquatic and terrestrial organisms in the higher stages of the food chain (carnivores, omnivores) are exposed to OMPs due to two factors: the consumption of organisms on the lower side of the food chain which have themselves consumed OMPs from mediums such as the soil, air, and water and the persistence of OMPs within these organisms. This results in a range of cases of consumption habits of OMPs for various organisms, which depends on the OMPs themselves (Okeke et al. 2022). Research has also been performed using mathematical models to measure the uptake of micropollutants of aquatic organisms from water versus the food chain

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(Thomann 1981). They measured the uptake of polychlorinated biphenyls (PCB), Plutonium-239 (Pu), and Caesium-137 (Cs). The research concluded that the update of PCBs in top predators was almost entirely through the food chain (due to the high environmental persistence of PCBs). In contrast, the uptake of Plutonium-239 in all organisms within the food chains was due to the uptake of water only, as Plutonium239 has low persistence in the food chain due to its radioactivity which allows organisms to immobilize and excrete it relatively efficiently (UNSCEAR 2000). The uptake of Caesium-137 was also mostly due to the food chain, however varied depending on the salinity-dependent phytoplankton adsorption, as the persistence of Caesium-137 in organisms is highly dependent on the metabolic processes within the specific organisms as well as their interactions with Caesium-137. This range of results explains the precise variability of pathways that OMPs use within the environment based on their properties and interactions within organisms (UNSCEAR 2000). It has been determined that the solubility of chemicals is an important factor in the pathways that are most effective for the distribution of the chemical in the environment. Generally, compounds with less solubility in water are found to be more persistent, bioaccumulative, and toxic as compared to compounds with higher solubility (La Farre et al. 2008). This allows for their detection in locations far away from their source. Comparatively highly soluble and highly transformable compounds can travel through mediums much faster and across a larger distance. These compounds can transform into more available forms due to metabolic processes and cannot be completely metabolized by animals, which leads to the excretion of their parent molecules in feces and urine. These compounds are more likely to enter organisms through mediums rather than food chains (Boxall et al. 2012). The bioaccumulation of OMPs such as pesticides occurs in fat tissue and is a major factor in their persistence within the ecosystem (Humphries et al. 2021). Food chains primarily perpetuate OMPs which have a high degree of persistence in tissue, such as several classes of pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons (PAHs), etc. Regardless of the pathways, the effects of these OMPs are still dangerous and deleterious to the organisms that are exposed to them.

5 Identification of OMPs Different methods, such as high-performance liquid chromatography (HPLC), QuEChERS (quick, easy, cheap, effective, rugged, and safe) method, LCMS (liquid chromatography-mass spectrophotometry), GCMS (gas chromatography mass spectrophotometry), NMR (nuclear magnetic resonance), etc., are frequently used to identify the organic micropollutants in various industries, including agriculture, pharmaceuticals, industry, etc. Identification of compounds is quite important to remediate the problems caused by micropollutants (MPs). Different studies were conducted with different techniques to identify such micropollutants (Żwir-Ferenc

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and Biziuk 2006; Debayle et al. 2008; Boligon and Athayde 2014; GonzálezCurbelo et al. 2015).

6 Conclusion and Future Prospects The present study focuses on the adverse impacts of micropollutants (MPs) on the environment and human health. Micropollutants may be categorized into several groups according to their characteristic features. Pesticide exposure can have numerous ill consequences on human health which leads to severe acute and chronic symptoms, long-term health issues, and effects on growth and development. The awareness concerning the harmful effects of OMPs has been accelerated in the last few years. These OMPs present in the atmosphere could attained least concern due to their low concentration in the environment. However, recent development in sophisticated analytical instruments/techniques exhibited a key factor in detection and identification of these pollutants. The knowledge of their persistence and toxicity can be used to deal with and to develop plan for their management. Various government and nongovernment organizations can also be formed to develop remedies based on scientific, managerial, and ethical basis and become proactive before these pollutants bring any severe environmental impairment. The needs are to: 1. Develop cost-effective methods for identification of various micropollutants and their metabolites. 2. The development of eco-friendly and cost-effective abatement technologies.

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Occurrence and Toxicity of Organic Microcontaminants in Agricultural Perspective: An Overview Hardik Giri Gosai, Foram Jadeja, Asha Sharma, and Shilpi Jain

Abstract Organic micro-pollutants (OMPs) are an increasing global concern that contaminate important environmental matrices. The OMPs in agriculture include di-(2-ethylhexyl)phthalate (DEHP), nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), and diethoxylates (NP2EO), polychlorinated biphenyl congeners (PCB), polycyclic aromatic hydrocarbons (PAH) and linear alkyl benzene sulphonates (LAS), microplastic (styrene-based polymer, polyesters, polyethylene, polypropylene, polyamide), organochlorine pesticides (OCPs) (like DDT, heptachlor, and aldrin), flunixin (veterinary drug), herbicides (Diuron, mecoprop, 2-methyl-4-chlorophenoxyacetic acid), and terbuthylazine (pesticides). OMPs enter the soil-water ecosystem via a variety of routes, including irrigation water in agricultural settings, the discharge of expired pharmaceuticals, the use of biosolids or animal excreta, sewage effluent, and industrial operations, among others. Furthermore, OMPs enter the food chain via a variety of pathways, including groundwater, agricultural soil, and irrigated water. All of these contaminants’ final host is soil, where soil microbes break them down biologically. Adding chemicals can speed up the process, but using physical methods to remove OMPs is expensive. These OMPs disrupt different soil biogeochemical processes, harm soil quality and microbial diversity, and cause genetic alterations in the microbial ecology. The persistence of the OMP raises the risk to human health as it moves up the food chain. Limitations on the release of new OMPs into the environment are not yet available to developing nations. This needs to be taken into consideration to establish limitations based on scientific evidence. This chapter focuses on the prevalence and concentration patterns of organic micro-pollutants (OMPs) in agricultural fields, as well as their routes of transfer to agricultural land and associated control measures.

H. G. Gosai (✉) · F. Jadeja · A. Sharma · S. Jain Department of Environmental Studies, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara, Gujarat, India e-mail: [email protected]; [email protected]; [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 R. Bhadouria et al. (eds.), Organic Micropollutants in Aquatic and Terrestrial Environments, https://doi.org/10.1007/978-3-031-48977-8_6

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Keywords Agricultural land · Contaminants · Impacts · Management strategies · Sources

Abbreviations DEHP LAS NP NP1EO NP2EO NPE OCPs OMPs PAH PCBs PCDD TCS

Di-(2-ethylhexyl)phthalate Linear alkyl benzene sulphonates Nonylphenol Nonylphenol mono-ethoxylate Nonylphenol di-ethoxylate Nonylphenol ethoxylates Organochlorine pesticides Organic micro-pollutants Polycyclic aromatic hydrocarbons Polychlorinated biphenyls Polychlorinated dibenzo-p-dioxins Triclosan

1 Introduction Organic micro-pollutants (OMPs) comprise chemical substances found in the surroundings with the amount ranging from μg/L to ng/L. These chemicals can sometimes even be found at much lower levels (Hollender et al. 2008). Every day, new steps forwards are taken in the process of evolution. In today’s modern culture, the needs of humans are met by the application of various chemical components. Many of these substances, which can be found in food, soil, water, and air, are hazardous to human health. Over time, OMPs have become important causes of pollution. Also at risk from these compounds are ecosystems, human health, and security. There are numerous types of OMPs, including microplastics, endocrine-disrupting compounds (EDCs), polycyclic aromatic hydrocarbons (PAHs), pharmaceuticals, personal care products (PCPs), agricultural goods, flame retardants, and industrial chemicals (Farré et al. 2008; Singh et al. 2021). In response to the severe food scarcity experienced by many developing countries in the 1950s, efforts were made to increase the productivity of vital grain crops such as maize, wheat, and rice, with the goal of improving food security and meeting the dietary needs of their populations. Short-stemmed hybrid grains that received a lot of fertiliser which performed well were developed by plant breeders. In especially throughout Asia, these hybrids demonstrated tremendous advances in terms of yield per hectare as well as overall grain production. The increased use of agricultural chemicals is largely responsible for the larger surpluses (Kendall and Pimentel 1994; Tripathi et al. 2020a).

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Concern among scientists over the presence of OMPs in agricultural land is growing over time. This is due to the possibility that some of these OMPs, if released onto agricultural land, could harm both the ecosystem and human health. Comprehensive studies have been conducted to detect the presence of OMP in various environmental matrices such as air, soil, and water, as well as its absorption into food chains. These research aim to uncover the toxicological implications of OMPs for both our surroundings and human beings (Babut et al. 2019). The application of organic residue to agricultural land improves soil organic matter content and water retention capacity significantly (Mylavarapu and Zinati 2009), easier soil tillage, a lessening of the impacts of salinisation in arid environments, and the growth of plant roots (Lakhdar et al. 2009). Organic waste incorporation in agriculture promotes carbon absorption within the soil, lowering atmospheric CO2 levels and minimising the risk of global warming (Boldrin et al. 2009). Organic matter incorporation into the soil improves soil structure, reduces susceptibility to plant diseases, and reduces erosion rates. In arid areas, where the soil frequently has little organic matter and has a poor ability to hold water, adding organic matter is very important (Cook 1986; Andreadakis et al. 2002; Escuadra and Amemiya 2008). The primary industries in agriculture are those that produce food, fibre, and fuel. The population of a country is supplied with its needs by agricultural operations. Food and energy demand has risen sharply in response to a considerable jump in population growth and industrial expansion over the last decade. As a result, there has been a shift away from natural agriculture and towards chemical-intensive practices (Khademi et al. 2019). OMPs are composed of a variety of chemicals, each of which belongs to a particular chemical class and has a particular purpose. Toxic, persistent organic pollutants (POPs) have a tendency to concentrate within the biota and flora and have the ability for long-distance atmospheric dispersion due to their resistance to degradation and strong hydrophobic properties (Olatunji 2019; Cindoruk et al. 2020). There have been widespread reports of the three major classes of POPs in the environment. Human-made compounds include polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs), and organochlorine pesticides (OCPs). Furthermore, this chapter will summarise the sources of organic micro-pollutants, as well as their impacts and treatment measures.

2 Sources of Organic Micro-pollutants (OMPs) in Agricultural Land Surface runoff, leaching, groundwater recharge, and other pathways can introduce organic compounds used in agriculture into the water cycle. Organic micro-pollutant (OMP) concentrations in aquatic environments have increased significantly due to developments in monitoring technologies, potentially influencing numerous biogeochemical processes such as biodegradation, denitrification, nitrogen fixation, and

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amination (Heberer 2002; Grung et al. 2015; Bai et al. 2022; Tripathi et al. 2020b). During the 1990s, there was a significant increase in the number of large-scale animal feeding operations (AFOs) dedicated to the rearing of pigs, poultry, and cattle (Browner et al. 2001). Drugs and feed additives are allowed in food-animal farming (Bloom 2004). Antibiotics for animals, often known as veterinary antibiotics (VAs), are routinely used to prevent illness and livestock damage in many countries. Furthermore, they are added to animal feed to increase productivity and decrease waste. Because antibiotics are only partially absorbed by the animal’s intestines, they remain mostly unaltered in the animal’s faeces (Sarmah et al. 2006). Since the 1960s, plant protection products (PPPs) including insecticides, fungicides, nematicides, herbicides, and soil fumigants have been used globally in response to the increasing demand for food production (Imfeld and Vuilleumier 2012). Reusing sewage sludge in agriculture, especially as fertiliser, is popular and can help the soil to retain water and nutrients, but it also poses a threat to the environment because it serves as a route for organic micro-pollutants. Furthermore, sewage sludge solids derived from wastewater could be seen as a sink for dangerous compounds (such as pathogens, heavy metals, and organic contaminants) that will accumulate in soils (Dichtl et al. 2007). Sewage sludge, leachates, municipal landfills, and animal dung used as organic fertiliser are all potential entry points for pharmaceuticals into agricultural land (Boxall 2004; Carter et al. 2014). Other than nonsteroidal anti-inflammatory medications, hormones, and antibiotics, organic micro-pollutants (OMPs) are frequently studied in wastewater for agricultural reuse. Personal care products (PCPs) such as perfumes and antioxidants, as well as additives used in a wide range of industrial products, are examples of organic micro-pollutants (OMPs). Chemicals present in wastewater treatment plant effluents are closely studied due to their tenacity and the possibility that they may interfere with endocrine function (Montesdeoca-Esponda et al. 2018). Wastewater becomes contaminated with new contaminants as a result of industrial discharge and domestic discharge. Several pollutants are still present in the effluent after being treated at conventional wastewater treatment plants. When utilised for irrigation, cleaned wastewater can introduce harmful chemicals into the agricultural land (Gani et al. 2021). The application of cow dung-derived manure is one of the primary mechanisms by which organic contaminants enter agriculture. The agricultural soil has been shown to have bacteria that are resistant to antibiotics. Cow manure contains antibiotic-resistant genes linked to common drugs including chloramphenicol, kanamycin, tetracycline, and beta-lactam. As cow manure comes into contact with cropland, it can propagate antibiotic-resistant genes (Wichmann et al. 2014). Antibiotics are found in high concentrations throughout agricultural soil as a result of manure application and management. The most common methods for introducing newly discovered pollutants into agricultural soil are the use of pesticides and medications (also known as veterinary medicines). Nearly all veterinary drugs end up in the soil via the animals’ faeces and urine (Durso and Cook 2014; Chen and Xia 2017). Figure 1 represents the different sources of OMPs in agricultural land.

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Fig. 1 Sources of organic micro-pollutants (OMPs) in agricultural land

Once OMPs are introduced into an agricultural setting, emerging contaminants exhibit the same fate and transit behaviour as other classes of pollutants. Emergent pollutants can be degraded via a variety of mechanisms, including biological, physical, and chemical processes, as well as plant adsorption. Furthermore, they may degrade during conveyance to surface fluids, overflow to drainage water, and percolation to groundwater. Table 1 summarises the concentration levels of several types of organic micro-pollutants (OMPs) observed in the agricultural land location.

3 Impacts of Organic Micro-pollutants (OMPs) 3.1

Impacts on Soil Biota

Inadequate pesticide application on crops and subsequent buildup in the soil might have a negative influence on soil fertility. These pollutants have the ability to stick to soil particles and stay in the soil for long periods of time, especially if they are deposited on the soil surface. Furthermore, crop pesticides have the potential to influence soil bacteria and disrupt the physiological and metabolic processes that they engage in. The unregulated use of these chemicals causes soil degradation and disrupts the ecosystem’s natural biogeochemical and elemental cycles (Savonen 1997). Penicillin is widely used and the impact of the antibiotic penicillin on bacteria that have been cultured has been investigated. It has a deleterious effect on the production of bacterial cell walls. Both tetracycline and streptomycin have an effect that is detrimental to bacterial growth. They interfere with the process by which bacteria produce ribosomal proteins (Zavarzin and Kolotilova 2001). The herbicide triclopyr is often used for landscaping purposes. It reduces the activity of bacteria that

Sr. no. 1

OMPs DEHP [di-(2-ethylhexyl) phthalate]

Agricultural soil from Yangtze River Delta Agricultural soils across the Yellow River Delta region

China

Spain

Area description Gopalganj, Bihar Perumbavoor, Kerala IARI, Delhi Yamuna Bank, Delhi Chaurali Village, Gautam Buddha Nagar, Uttar Pradesh Achheja Village, Gautam Buddha Nagar, Uttar Pradesh Cooch Behar, West Bengal Tinsukia, Assam Thakurain Tola Village, Chhattisgarh Saharanpur, Uttar Pradesh Cuttack, Orissa Amarkantak, Madhya Pradesh Tea Garden, Assam Allahabad, Uttar Pradesh Banda, Uttar Pradesh Lucknow, Uttar Pradesh Shahdol, Madhya Pradesh Biosolid samples

Country India

Table 1 Concentration of organic micro-pollutants (OMPs) in agricultural land

0.433–11.488 mg/kg

4.11–1510 ng/g

403.622 ng/g 253.746 ng/g 572.381 ng/g 488.068 ng/g 194.892 ng/g 253.855 ng/g 644.387 ng/g 307.626 ng/g 390.019 ng/g 552.316 ng/g 318.647 ng/g 4.91–15.8 mg/kg

722.628 ng/g

Reported concentration 1133.574 ng/g 8559.511 ng/g 1655.189 ng/g 485.411 ng/g 455.575 ng/g

Martín et al. (2022) Wei et al. (2020) Sun et al. (2023)

Reference Saha et al. (2022)

112 H. G. Gosai et al.

2

NP (nonylphenol)

China

India

Taiwan

Gopalganj, Bihar Perumbavoor, Kerala IARI, Delhi Yamuna Bank, Delhi Chaurali Village, Gautam Buddha Nagar, Uttar Pradesh Achheja Village, Gautam Buddha Nagar, Uttar Pradesh West Bengal Tinsukia, Assam Thakurain Tola Village, Chhattisgarh Saharanpur, Uttar Pradesh Cuttack, Orissa Amarkantak, Madhya Pradesh Tea Garden, Assam Allahabad, Uttar Pradesh Banda, Uttar Pradesh Lucknow, Uttar Pradesh Shahdol, Madhya Pradesh Jhansi, Uttar Pradesh Varanasi, Uttar Pradesh Bareilly, Uttar Pradesh Hooghly, West Bengal Leh, Ladakh

Kaohsiung city

0.574 ng/g 0.324 ng/g 0.720 ng/g 0.398 ng/g 0.353 ng/g 0.498 ng/g 0.811 ng/g 0.611 ng/g 0.325 ng/g 10.218 ng/g 0.984 ng/g 1.052 ng/g 0.749 ng/g 0.740 ng/g 6.354 ng/g 0.980 ng/g 0.126–22.9 mg/kg

0.913 ng/g

7.631 ng/g 0.337 ng/g 1.550 ng/g 0.665 ng/g 1.832 ng/g

0.7 ± 0.5 mg/kg

(continued)

Hu et al. (2021)

Kaewlaoyoong et al. (2018) Saha et al. (2022)

Occurrence and Toxicity of Organic Microcontaminants in. . . 113

4

3

Sr. no.

NP2EO (nonylphenol di-ethoxylate) TCS (triclosan)

NP1EO (nonylphenol mono-ethoxylate)

OMPs

Table 1 (continued)

Vegetable farms, Pearl River Delta, South China Biosolid sample

China

India

Spain

Spain

Gopalganj, Bihar Perumbavoor, Kerala IARI, Delhi Yamuna Bank, Delhi Chaurali Village, Gautam Buddha Nagar, Uttar Pradesh Achheja Village, Gautam Buddha Nagar, Uttar Pradesh Cooch Bihar, West Bengal Tinsukia, Assam Thakurain Tola Village, Chhattisgarh Saharanpur, Uttar Pradesh

Vegetable farms, Pearl River Delta, South China Biosolid sample

China

Spain

Area description Experimental station of the National Center for Efficient Irrigation Engineering and Technology Research—Beijing Biosolid sample

Country

142.793 ng/g 167.495 ng/g 20.106 ng/g 228.596 ng/g

40.648 ng/g

4.941 ng/g 13.303 ng/g 921.570 ng/g 28.231 ng/g 31.336 ng/g

8.68–20.1 mg/kg

8.24 μg/kg

0.93–2.79 mg/kg

7.22 μg/kg

10.6 mg/kg

Reported concentration

Saha et al. (2022)

Martín et al. (2022)

Martín et al. (2022) Cai et al. (2012)

Martín et al. (2022) Cai et al. (2012)

Reference

114 H. G. Gosai et al.

5

PAH (polycyclic aromatic hydrocarbons)

223–8214 ng/g 294–1665 ng/g 33.5–426.9 ng/g

Agricultural soil

East of Oran (Northwest Algeria)

Shanghai

Agricultural soil, Shanxi

Agricultural field

Pakistan

Azerbaijan

Algeria

China

Lebanon

33–2934 ng/g

Mambakkam and Cheyyar SIPCOT belt, Tamil Nadu Agricultural soil, Chakera, Faisalabad

India

133.72–249.69 ng/g

0.15–16,026 mg/kg

8.28–11.65 ng/g

122.52 μg/kg

Bhopal, Madhya Pradesh

West Africa

23.930 ng/g 22.720 ng/g 147.288 ng/g 7.847 ng/g 25.216 ng/g 10.360 ng/g 18.100 ng/g 7.592 ng/g 7.122 ng/g 1.861 ng/g 24.267 ng/g 36.6–1142 ng/g

Cuttack, Orissa Amarkantak, Uttar Pradesh Tea Garden, Assam Allahabad, Uttar Pradesh Banda, Uttar Pradesh Lucknow, Uttar Pradesh Shahdol, Uttar Pradesh Jhansi, Uttar Pradesh Varanasi, Uttar Pradesh Hooghly, West Bengal Leh, Ladakh Sierra Leone

(continued)

Janneh et al. (2023) Yadav et al. (2020) Selvaraj et al. (2021) Mahfooz et al. (2022) Ukalska-Jaruga et al. (2020) Halfadji et al. (2019) Tong et al. (2018) Duan et al. (2015) Soukarieh et al. (2018)

Occurrence and Toxicity of Organic Microcontaminants in. . . 115

6

Sr. no.

OCPs (organochlorine pesticides)

OMPs

Table 1 (continued)

Shabankare and Dalaki, Bushehr Province, south of Iran

Iran

Pakistan

Owhrode, Uwheru, Obiaruku, Aboh, Owhelogbo, and Oleh (Southern Nigeria)

Mambakkam and Cheyyar SIPCOT belt, Tamil Nadu Agricultural soil Polish agricultural soil Agricultural surface soils from southeastern to central-western part

Area description Ulsan

Nigeria

Azerbaijan Poland Tanzania

India

Country Korea

0.01–21,888 mg/kg 4.03–1037.59 μg/kg ΣDDTs (p,p′-DDE; p,p′-DDT; p, p′-DDD; o,p′-DDT; o,p′-DDD; o, p′-DDE) Methoxychlor Heptachlor Aldrin ΣDDTs (p,p′-DDE; p,p′-DDT; p, p′-DDD) Methoxychlor Heptachlor Aldrin Heptachlor Aldrin ΣDDTs (o,p-DDE, o,p-DDD, o, p-DDT, p,p-DDE, p,p-DDD, p, p-DDT, and DDT) ΣCHL (trans-chlordane, cis-chlordane, heptachlor exo-epoxide, and heptachlor) Aldrin

81.4 ng/g

Reported concentration 65–12,000 ng/g

2.04 ng/g

45.6 ng/g 53.4 ng/g 48.3 ng/g 113 ng/g 5.80 ng/g 4.37 ng/g

4.9 ng/g 0.84 ng/g 0.49 ng/g 63.5 ng/g

47.44 ng/g

Kafaei et al. (2020)

Tesi et al. (2020)

Nyihirani et al. (2021)

Reference Kwon and Choi (2014) Selvaraj et al. (2021) Ukalska-Jaruga et al. (2020)

116 H. G. Gosai et al.

LAS (linear alkyl benzene sulphonates) Microplastic

8

9

PCBs (polychlorinated biphenyls)

7

2.0–148.5 ng/g 1.23–3.67 ng/g

Hexi corridor East of Oran (Northwest Algeria)

Bhopal, Madhya Pradesh

Agricultural soil Agricultural soil

Agricultural soil

Agricultural soil, Yeoju City

China Hungary

Thailand

Korea

Biosolid samples

64.3–4358 pg/g

664 pieces/kg

12–17 items/m2

4.94 items/kg 225 ± 61.69 pieces/kg

752.5 ± 6.36 particles

67.9–3647 mg/kg

180 ng/g

88.0–293 mg/kg

0.02–147.30 μg/kg

0.3–9 ng/g

Methoxychlor

Heptachlor

Soil from selected telecom masts in the Niger Delta Top layer soil of crops, Chakera, Faisalabad Agricultural soil

Mambakkam and Cheyyar SIPCOT belt, Tamil Nadu Agricultural soil

India

Spain

Algeria

China

Pakistan

Nigeria

Azerbaijan

India

Top layer soil of crops, Chakera, Faisalabad

1.7–6.1 ng/ g 1.6–5.2 ng/ g 5.1–15 ng/ g

(continued)

Singh et al. (2023) Tang (2023) Sa’adu and Farsang (2022) Fakour et al. (2021)

Selvaraj et al. (2021) Ukalska-Jaruga et al. (2020) Emoyan et al. (2022) Mahfooz et al. (2022) Mao et al. (2021) Jia et al. (2023) Halfadji et al. (2019) Martín et al. (2022)

Mahfooz et al. (2022)

Occurrence and Toxicity of Organic Microcontaminants in. . . 117

Sr. no.

OMPs

Table 1 (continued)

China

Agricultural soils from the Yangtze River Delta Agricultural soil of Shanghai

Agricultural land of Gaidahawa rural municipality European agricultural top soils

Nepal

Netherlands

Polish agricultural soil

0.05–90.8 ng/g

Agricultural sites

Poland

0.089 ng/g

Agricultural site

South Africa

3.16 to 265.24 ng/g

500 μm) can be analyzed using ATR-FTIR, whereas smaller microplastic fractions can be analyzed by coupling FTIR with a microscope called a micro-FTIR. Quantification and identification of fine contaminants within the mixed samples can be done in the FTIR transmission mode as it yields high-quality spectra data. However, it requires a transparent infrared substrate. In addition, the investigated particles must be sufficiently thin ( stem > root. The OMPs may be absorbed in large quantities by the organisms that live on or are fed by these plants, much like persistent organic pollutants. For instance, it has been observed that three food levels of the ecological food chain in the waters of the Columbia River are biomagnified by endocrinedisrupting chemicals (EDCs), including flame retardants made of polybrominated diphenyl ether (PBDE) (Rayne et al. 2003). Furthermore, because many bacteria found in plants have activities that promote plant growth, inhibiting microflora may weaken a plant’s ability to defend itself against contaminants. The reactive oxygen species (ROS) production in food may have an impact on the health of advanced animals, counting people who eat the plant directly (Choe and Min 2005). In addition to harming plants and microorganisms, OMPs can also indirectly harm animals, particularly through the consumption of macroinvertebrates in the food chain. For instance, it was discovered that PBDE flame retardants, whose concentration was not particularly high in invertebrate biomass, were biomagnified in osprey eggs and large-scale suckers (Nilsen et al. 2014). The OMPs are chemical substances, making them unavoidable in the environment and posing danger along all conceivable hazard pathways. Due to these chemicals’ propensity to accumulate, degrade, reassemble, and undergo novel transformations when exposed to particular environmental conditions, their existence could cause bioaccumulation and have potentially harmful effects at different levels of the alimentary web.

6.2

Genotoxicity

Chronic OMP exposure can cause genotoxicity, which can include chromosomal rearrangements, point mutations, insertions, inversions, and deletions, as well as long-lasting epigenetic modifications (phosphorylation, DNA methylation, and histone modifications) (Hoffmann and Willi 2008). These mutation alterations are foremost influenced by the contaminant’s potential for toxicity and length of exposure. Due to the fact that many OMPs are made to control metabolic processes, prolonged exposure to them may disrupt the organism’s genome. Numerous studies have documented genetic changes brought on by chemical exposure in plants and animals as well as in lab and field settings (Dixon et al. 2002). Additionally, genotoxicity may affect both somatic and germinal cells; as a result, negative effects may manifest within the same generation or across generations, as appropriate. While cell genotoxicity can cause harm to the following generation, somatic cell genotoxicity can cause physiopathological changes that can lower the median efficiency of the afflicted group by impairing vital metabolic functions, similar to how active metabolites can alter epigenetic patterns over time. An antihypertensive

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drug called hydralazine, for instance, has been shown to prevent DNA methylation, which leads to unrestrained gene expression. In a recent study, a drug’s two-tiered effects were assessed. Initial exposure had significant effects on signaling pathways, altering the activity of transcription factors at the promoter region of genes, while chronic exposure led to more significant long-term changes in chromatin structure and DNA methylation. Additionally, even after the drug was stopped, the epigenetic changes persisted (Csoka and Szyf 2009).

7 Remediation Techniques and the Possibility of Their Removal 7.1

No Biological Remediation Techniques

Activated carbon adsorption, hydrostatic exclusions, membrane ultrafiltration, and electrostatic limitations are a few traditional and contemporary nonbiological approaches for OMP cleanup (Ojajuni et al. 2015). Advanced oxidation is a type of water-based oxidation process that may eliminate a variety of OMPs, mostly using mineralization by producing highly reactive species or by adapting them to fewer hazardous compounds (Tawabini 2014). The use of ozonation, ultrasound, Fenton’s reaction, moist air oxidation, and photocatalysis based on near-ultraviolet or solar visible irradiation is a crucial tactic (Ikehata et al. 2008). Fenton’s reagent, microwaves, pulsed plasma, ionizing radiation, and other newer theories have also been considered to be creating oxidation processes. Although the method has been quite popular for removing OMPs, it has limits when the effluents include larger concentrations of organic and/or inorganic debris. Activated carbon adsorption is a viable solution to the issue of coping with an effluent with high levels of organic matter since the pollutants’ hydrophobic character (compounds with Kow 27 days and SRT >35 days might obtain the maximum elimination (Servos et al. 2005).

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9 Conclusions and Future Perspectives Organic micro-pollutants (OMPs) are becoming more widely recognized as a significant class of emerging pollutants. Due to their low environmental concentrations, these chemicals are everywhere but almost never draw attention to themselves. Moreover, due to their low environmental concentrations, these compounds are omnipresent yet practically never draw attention to themselves. This relatively new perspective is mostly due to the sophisticated analytical methods required to discover these chemicals at such low quantities. The list of OMPs and their environmental impacts may be documented using an inventory of the current literature. Such an inventory may provide details on the interactions and ultimate fate of metabolites in environments. Understanding persistence, toxicity, and leachability at both the simple and complex levels might help us foresee and get ready for possible coercions. Here are a few potential directions this field could go in the future. • We believe that before OMPs can cause any serious environmental impairment, the global authorities in charge of ecological safety and environmental integrity must show concern and take preventative action. • It is crucial to have a deeper understanding of the environmental toxicity significance of different chemicals in the class of OMPs and develop cost-effective management strategies, and the establishment of reliable and affordable detection and analysis techniques is essential. • Before moving on to risk assessment and control, it is crucial to assess the environmental fate of the risk management plan. Finding safer OMPs to replace the most harmful one could be a major advance. Practical risk assessment techniques should be considered in the meantime for the evaluation of bioactive OMPs. It is time to implement a multi-nutritive environmental risk assessment (ERA) approach, just as we evaluate synthetic agrochemicals and pesticide proteins produced by genetically modified crops for commercial distribution.

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Methodologies for the Detection and Remediation of Organic Micropollutants in Terrestrial Ecosystems Jatinder Singh Randhawa

Abstract At present, most of the terrestrial ecosystems are highly contaminated, due to continuous discharge of a diverse range of organic micropollutants (OMPs) from different sources in the environment without adequate treatment. Considering the detrimental impacts of OMPs on both the environment and human health, treatment is imperative before discharge. To treat the continual emissions of OMPs (including personal care products, pesticides, heavy metals, dyes and pharmaceutical active compounds), various methods such as adsorption, coagulation, flocculation, ozonation, electro-oxidation and electro-coagulation were continually proposed and implemented. So far various conventional methods for OMP degradation have been studied extensively, but failed due to its expensive and inefficient nature. To overcome the drawbacks associated with these existing methods, these can be replaced by environmentally safer and cost-effective methods. Biological treatment methods are capable of efficiently removing OMPs even at lower and higher concentrations in an environmentally safer and cost-effective manner. Numerous microorganisms, including bacteria, fungi, algae and the enzymes released from these microorganisms, have recently been used in biological methods for the remediation of OMPs. To give significant insight into the technology used for the removal of OMPs, this chapter comprehensively reviewed the current removal methods, mechanisms and comparisons of methods with their advantages and disadvantages as well as future outlooks and recommendations. Keywords Bioremediation · Degradation · Discharge · Environment · Human health · Micropollutants

J. S. Randhawa (✉) Regional Water Testing Laboratory, Department of Water Supply and Sanitation, Amritsar, Punjab, India © The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 R. Bhadouria et al. (eds.), Organic Micropollutants in Aquatic and Terrestrial Environments, https://doi.org/10.1007/978-3-031-48977-8_8

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Abbreviations AOP GAC GC HPLC HRMS LC mg/L MS ng/L NOMs o-DGT OMPs PAC PAHs PCPs PhACs POCIS SPE VEC WW

Advanced oxidative processes Granular activated carbon Gas chromatography High-performance liquid chromatography High-resolution mass spectrometry Liquid chromatography Milligrams per litre Mass spectrometry Nanograms per litre Naturally occurring matter Organic-diffusive gradients in thin films Organic micropollutants Powdered activated carbon Polycyclic aromatic hydrocarbons Personal care products Pharmaceutically active compounds Polar organic chemical integrative sampler Solid-phase extraction Vacuum-assisted evaporative concentration Wastewater

1 Introduction A worldwide issue endangering life on earth is the emission of ecotoxicological substances, particularly organic micropollutants. Micropollutants also known as trace organic contaminants (TrOCs) may exist in the environment at concentrations as small as a few nanograms per litre (ng/L) and as large as several milligrams per litre (mg/L) (Huerta-Fontela et al. 2011). Their negative impacts on human health, the environment and aquatic life have not yet been thoroughly studied and in certain cases, they are totally unknowable (Barbosa et al. 2016). These micropollutants include common home items, medications, industrial chemicals, personal care items, dyes, surfactants, pesticides, flame retardants and metallic trace elements as depicted in Fig. 1. They also include polycyclic aromatic hydrocarbons (PAHs), endocrinedisrupting substances and medicines. The majority of dyes are found in the wastewater (WW) from the textile industry (Yaseen and Scholz 2019). In addition, heavy metals are frequently utilised as catalysts to create various colour intermediates in the textile industries (Noreen et al. 2017). Furthermore, significant amounts of heavy metals have been found in home WW and municipal soil (Kanmani and Gandhimathi 2013). In addition, Sathishkumar et al. (2021) found that sewage from hospitals and agro-industrial leftovers are the most common places to detect

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Pesticides

PAHs

Dyes

Heavy metals

Micro pollutants

EDCs

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PPCPs

Surfactants

POPs

Fig. 1 Primary micropollutants in the environment. EDCs endocrine-disrupting chemicals, PAHs polycyclic aromatic hydrocarbons, POPs persistent organic pollutants, PPCPs pharmaceuticals and personal care products

organic matter, pesticides and pharmaceutically active compounds (PhACs). Environmental scientists are focusing on efforts to lessen the negative effects of these micropollutants present in the environment. This is because these micropollutants are constantly accumulating in our surroundings and are widely available (Hadibarata et al. 2019; Hu et al. 2020; Ishak and Malek 2021). As presently, the majority of researchers suggest that wastewater treatment facilities are the primary source of organic micropollutants (OMPs) in aquatic bodies, whereas manure, sludge, urban runoff and other sources of treated and untreated wastewater application are the main sources of OMPs in soil. Through leaching or runoff, soil OMPs are released into water bodies and may harm the aquatic life (Abbasi et al. 2022). Groundwater, open water bodies and soil environment pollution are all connected and may have adverse cumulative impacts on aquatic creatures over several generations and adversely impact human health, being a part of the ecosystem (Daughton 2010). The environment may be adversely impacted by the perpetual discharge of such pollutants without adhering to regulatory requirements. According to the findings of several studies, they might be harmful to the environment, human health, the food chain and microbes. Therefore, control techniques (both for prevention at source and cleanup of polluted places) are needed to handle such a scenario. Micropollutant contamination and emission might result in serious harm if necessary action is not done. To remove micropollutants, specialists have developed a number of physical and chemical techniques. However, they are either costly or not environment friendly (Sattar et al. 2022). Numerous methods, including adsorption (Jasni et al. 2017; Syafiuddin et al. 2019; Chen et al. 2020), electro-oxidation (Hu et al. 2020; Wirzal et al. 2021), flocculation (Chen et al. 2017), ozonation (Wen et al. 2018) and coagulation (Syafiuddin and Boopathy 2021), are utilised for remediation of these pollutants. Chemicals that are not environmentally friendly are

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needed for chemical coagulation and composite material adsorption because their residuals can directly and indirectly harm the environment. According to CuerdaCorrea et al. (2020), electro-oxidation, ozonation and electro-coagulation applications all need significant amounts of energy. Environmentally friendly biological therapies should be used in place of the current ways to address these problems. In contrast, biological remediation of micropollutants includes bioremediation, phytoremediation, phycoremediation and enzymatic degradation which are not only effective but also less expensive and ecologically responsible. Recent studies also recommend using biological remediation methods to eliminate environmental micropollutants (Ratnasari et al. 2021; Syafiuddin et al. 2021; Sattar et al. 2022). Recently, a range of biological methods employing fungi, bacteria and algae have been utilised to eradicate micropollutants (Adnan et al. 2016; Al Farraj et al. 2019; Syafiuddin et al. 2020, 2021; Ratnasari et al. 2021). Algae perform better remediation than bacteria and fungi, because they have polysaccharides in their cell walls that may absorb micropollutants (Synytsya et al. 2015). Algae also have relatively high levels of effectiveness, surface area and binding affinity. The usage of algae is basically straightforward and effective for eliminating pollutants such as textile dyes, PhACs, heavy metals and organic debris within the classification of biological therapy. Additionally, it is regarded as a cost-effective strategy for both manufacturing and upkeep. Additionally, it produces useful products, capable of growing with inorganic phosphate and nitrogen, and can produce biofuel though having a high level of environmental resistance (Papazi et al. 2019). It also provides inexpensive and plentiful energy via the photosynthesis process (Papazi et al. 2019). Environmental engineers and scientists have used a range of biological and physicochemical mechanisms for micropollutant degradation or removal. Traditional and cutting-edge biological approaches for micropollutant removal have been fully examined in the chapter’s first section, while the later section emphasises the value of various physicochemical techniques. This chapter discusses the removal effectiveness of several procedures against various micropollutants in addition to providing a quick overview of the operational specifics of the processes. The chapter also provides a summary of several significant research that employed biological, physical and chemical processes as a kind of therapy.

2 Analytical Techniques for Organic Micropollutant (OMP) Evaluation In order to validate the existence of the tested substances in a complex organic extract, the identification of OMPs necessitates particularly sensitive analytical techniques. Such diverse aquatic systems have an extensive variety and concentration of chemical substances, making quality monitoring difficult. High-end equipment can be employed in this discipline, like gas chromatography (GC) and liquid chromatography (LC) coupled with mass spectrometry (MS). These analytical

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techniques are frequently employed in these detection approaches to determine and quantify water pollutants like OMPs (Koutsouba et al. 2003; Ollers et al. 2001; Vanderford et al. 2003). They allow for the sub-ng/g level determination of OMPs from various matrices (Hao et al. 2007). Both LC-MS and GC-MS have a variety of drawbacks and benefits. To get the greatest results, using the right analytical methods is of utmost significance. The kind of sample and its complexity are important considerations for selecting the optimal approach. A unique benefit of LC-MS analysis is that pharmaceuticals are made up of polar molecules which are soluble in polar solvents and water. Personal care items (PCIs), on the other hand, are largely non-polar. Additionally, they are more extractable and soluble in organic solvents that are comparatively non-polar. OMPs may be detected in environmental samples at very low levels using the highly effective technique GC-MS (Hao et al. 2007). High-resolution mass spectrometry (HRMS) and other full-spectrum acquisition methods have recently been used to enable the screening for a variety of micropollutants (Hernández et al. 2019). The capture of complete spectrum by HRMS allows for the evaluation of the existence of many other chemicals in addition to those that were targeted initially. In LC-HRMS techniques for the identification of multiple distinct families of pollutants in aquatic settings, orbitrap and time-of-flight (TOF) analysers have been frequently employed (Pugajeva et al. 2017; CamposMañas et al. 2019). In addition to LC-MS techniques, GC-MS enables analysis of several volatile pollutants. Techniques for general and non-selective sample preparation are needed for the use of HRMS detectors that can measure a wide variety of chemicals. These processes frequently involve freeze-drying and are followed by solid-phase extraction (SPE), mixed-bed multilayer SPE and offline solid-phase extraction (SPE) using traditional sorbent material such as C-18, and mixed-mode (Gago-Ferrero et al. 2018). In other investigations, a large-volume direct injection method was used with an online SPE phase included but without clean-up step (Schollée et al. 2018). Vacuum-assisted evaporative concentration (VEC), which was recently introduced, has been effectively used to prepare samples for 590 organic components from wastewater (Mechelke et al. 2019). This environmentally safe method, which uses lesser organic solvents than SPE and is suited for extremely polar analytes, might be used as a substitute for SPE. Several studies have used passive sampling techniques based on the use of polar organic chemical integrative samplers (POCIS), organic-diffusive gradients in thin films (o-DGT) and passive sampler for the precise assessment of polar organic pollutants (mainly pharmaceuticals) that are suspected or targeted in wastewater (Alygizakis et al. 2020). The next sections provide an extensive description of the remediation methods of OMPs through conventional, biological, enzymatic and emerging technologies.

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3 Remediation Techniques for the Organic Micropollutants (OMPs) Conventional treatment methods including coagulation, flocculation, filtration and oxidant chemical treatment are ineffective against OMPs. The primary factors in OMP effectiveness as pesticides and environmental persistence are their chemical features, which include stability to all degradation processes, high fat and low water solubility and low vapour pressure (Katsoyiannis and Samara 2004). Scientists have developed alternative techniques as a result of the failure of standard procedures to completely eliminate OMPs from wastewater (WW) in some cases. OMPs have been treated utilising a variety of sophisticated WW treatment methods, involving membrane bioreactor-based biodegradation, activated carbon adsorption and advanced oxidation processes (Katsoyiannis and Samara 2004; Baêta et al. 2013; Cuerdacorrea et al. 2020). This is due to the increasing number of new OMPs that are found in water and the worries that come along with environmental and human health risks. Advanced techniques and technologies have lately been used to overcome a number of drawbacks, including expense, specialised instrumentation, limited degrading efficiency, creation of harmful secondary compounds and significant sludge production. Water treatment systems using enhanced adsorption, oxidation and biodegradation process are briefly discussed below (Alharbi et al. 2018).

3.1

Adsorption Process

In drinking water treatment facilities, using adsorption onto granular and powdered activated carbon (GAC and PAC), micropollutants are partly removed from surface water sources using fixed-bed filters (Piai et al. 2020). Before developing this technique for modular systems, various pilot filters filled with activated carbon were investigated. For instance, treatment with GAC is appealing for the eradication of a variety of OMPs since its high adsorption capacity and both the surface area and the absence of by-product generation. However, there are several difficulties which modular system designers must overcome, such as the high-energy consumption of the regeneration process as a result of the GAC’s ground-breaking adsorption capability. In order to address these issues, Altmann et al. (2016) investigated the purification of drinking water utilising both methods of GAC adsorption and bed filtration to remove OMPs and phosphorus. Companies that develop mobile adsorber and module systems also provide a wide range of equipment servicing options, such as transportation for spent carbons to reactivation facilities. PhACs, PCPs, EDCs and organic materials from decomposing plants as well as other naturally occurring matter (NOMs) can be removed using mobile adsorbers that are packed and carried on specific trailers made for food grade or industry versions. According to Streicher et al. (2016), the GAC method can also remove by-products and leftover compounds that result from the incomplete degradation of OMPs and lessen the severe toxicity

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of partly active OMPs. With the addition of PAC (10-min contact time) and coagulation dosage of 5 mg/L, the highest removal efficacy for the targeted OMPs (such as perfluorooctanoate and perfluoro-octane sulfonate) was attained (Abegglen and Siegrist 2012).

3.2

Biodegradation

In order to improve water and soil quality, biodegradation is a developing technique that uses certain live microbes to break down, metabolise and immobilise undesired compounds including pesticides, organic pollutants and hydrocarbons (Ojuederie and Babalola 2017). Even while every microbe has the capacity to eliminate contaminants, only a small number of specialised or modified microorganisms are widely utilised to do so (Kumar et al. 2020a, b; Singh et al. 2021). When used in the context of removing OMPs, bioremediation technology considers the technology listed below: (1) Bioventing: Water is aerated using bioventing to promote bioremediation and in situ biodegradation of organic contaminants; (2) biostimulation: Modifying polluted medium to enhance the ratio of C/N/P by adding limiting nutrients and altering pH in order to feed soil microorganisms; and (3) bioaugmentation: Adding bacteria, fungi and any other biocatalysts (genes and enzymes) to break down organic and inorganic contaminants (Gaur et al. 2018). The selection of microorganisms is one of the most crucial factors in the effective breakdown of petrochemical wastes in a certain environment. It is because only those microbes have been evolved to thrive in that particular environment. Similar to this, intermediates are produced while photocatalytic degradation operations are dangerous to a range of environmental organisms (Singh and Borthakur 2018). Currently, the membrane bioreactor performs poorly in the treatment of OMPs as well as the elimination of halogenated organic chemicals, pesticides, dyes and phenol derivatives as well as non-biodegradable aliphatic and aromatic hydrocarbon compounds. Technicality of the process and economic feasibility are the two key evaluation criteria for attaining the objective in WW treatment technologies (Badmus et al. 2018).

3.2.1

OMP Degradation by Enzymes

As indicated previously, ligninolytic enzymes such as laccases can be used directly to increase OMP breakdown rather than to promote microbial population in a variety of environmental conditions (Majeau et al. 2010). The following list of criteria pertains to direct application: (1) there could not be an effective enzyme for a given system’s OMPs and (2) inhibitors may alter the expression of the catabolic genes in microorganisms. The expression of microorganisms is regulated by a range of factors. Therefore, compared to bioaugmentation, direct administration of microbial extracts might have favourable effects in these

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circumstances. The use of such enzymes can thereby polymerise, oxidise or change a range of phenolic chemicals into less hazardous molecules. Such enzymes have a wide spectrum of substrates that include dyes, endocrine-disrupting compounds (EDCs), pesticides, polycyclic aromatic hydrocarbons (PAHs) and phenols. The production of laccase has frequently been accomplished utilising various fungi and microbes. Fungi produce laccase depending on a variety of factors, including the species, growing method, agitation and oxygenation. However, the concentration of nitrogen, glucose source proportion and the kind and amount of the inducer are the most important variables. An illustration of a semi-synthetic culture growth medium is a solid lignocellulosic waste in a synthetic liquid medium (Majeau et al. 2010). Because of their exceptional lignin-degrading ability, basidiomycetes species are among the microorganisms that have been the subject of substantial research for laccase synthesis. Numerous species have been shown to produce laccase exclusively or mostly as a ligninolytic enzyme; this trait is sometimes seen as advantageous since it can make purifying processes for commercial applications simpler. Other organisms that can produce laccase include Pleurotus ostreatus, Marasmius quercophilus, Trametes versicolor, Pleurotus pulmonarius, Ganoderma adspersum, Pycnoporus cinnabarinus and Pycnoporus sanguineus (Farnet et al. 2000; Pointing and Vrijmoed 2000; Hou et al. 2004; Singh et al. 2020). Moreover, a higher concentration of ligninolytic enzymes may be required to remove one or more OMPs from WW in order to increase decontamination effectiveness. The use of (1) pure free enzyme, (2) purified immobilised enzyme, (3) enzymes produced from culture broths and (4) bioremediation using reactors utilising immobilised or free cells can all enhance laccase’s efficacy in the removal of OMPs. Prior research has mostly concentrated on the purified laccase’s ability to oxidise a range of pollutants; nevertheless, practical WW treatment must still be optimised. Numerous phenolic substances have been proven to prevent the growth of the white-rot fungus, which has been observed to decrease total yield (Buswell and Eriksson 1994). Despite their immense potential, we currently know very little about the factors that control the synthesis of these enzymes in microbes (Majeau et al. 2010). Additionally, it has been shown that the enzymatic breakdown of a number of phenolic compounds produces unintended by-products that are much more toxic than the original compounds. Therefore, enzymatic degradation requires careful consideration. Before using OMPs at larger scales, it is also vital to analyse the risks associated with them and their by-products. Regarding the high costs of enzyme synthesis, there is not much information accessible. In this context, it has been noted that lignocellulosic waste may serve as a source for developing laccase-producing microbial cultures (Lorenzo et al. 2002; Howard et al. 2004). Still, more investigation is required to fully understand their potential in terms of the cost-effective synthesis of these enzymes.

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3.2.2

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OMP Degradation by Microalgae

According to several research organisations throughout the world, there are certain uses of live algae for the elimination of micropollutants (organic debris, dyes, heavy metals and PhACs). Chlorella vulgaris, a green alga, was used to remove waste effluent colour with 75.7% effectiveness (El-Kassas and Mohamed 2014). In addition, C. vulgaris was used to remove 41.8 to 50% of Supranol Red 3BW (Lim et al. 2010). The accumulation of dye ions had been linked to the elimination of dye through the biodegradation pathway. Essentially, there are three distinct procedures that may be used to remove dye from live algae. These processes involve the assimilation of chromophores to generate algae, the conversion of coloured to non-coloured molecules from H2O and CO2 and the adsorption of chromophores by algae. According to El-Kassas and Mohamed (2014), a series of biosorption, bioconversion and biocoagulation processes led to the decolorisation. The adsorption equilibriums between the isotherm constant and the adsorption type at different temperatures may be connected to this process. These results proved the effectiveness of C. vulgaris, a live alga, in removing dye from environmental matrices. Galdieria sulphuraria was the subject of a research to determine how well it removed phosphate while taking into account a variety of algae (Henkanatte-Gedera et al. 2015). After 3 days of exposure, G. sulphuraria was able to remove phosphate with an efficiency of up to 98% at a volumetric removal rate of 3.6 mg/L/day. Chlamydomonas reinhardtii was shown to remove 95% of the total phosphorus, according to another research (Lee et al. 2020). The effectiveness of removing organic debris was shown to heavily rely on both direct and indirect effects. Algal absorption of chemicals was the direct process, while the harvested biomass was the indirect mechanism. Contrarily, the indirect processes involved the vaporisation of ammonia and nitrogen as well as the precipitation of orthophosphate (Hena et al. 2021). The high pH created by algal photosynthesis, which is caused by these indirect pathways, may be observed. In light of this, the rate of algae growth reflects the effectiveness of phosphate and nitrogen removal. This discovery led to the conclusion that the maximum algal production under ideal conditions was one of the crucial factors for efficient organic matter removal (Olguın 2003). Additionally, differing algal culture compositions and organic materials in WW may lead to various organic matter removal processes (Su et al. 2012). Additionally, the adsorption of heavy metals from WWs using living algae was a popular practice. According to Ju et al. (2016), G. sulphuraria can remove >90% of palladium (Pd), gold (Au), copper (Cu(II)) and lanthanides (La(III)). Other types of algae, including Galdieria, had also demonstrated admirable heavy metal removal efficiency from WWs. As an example, Gracilaria sp. (51.5%), Ulva intestinalis (35.2%), Fucus vesiculosus (37.8%) and Ulva lactuca (31.8%) eliminated more than 30% of lead (Pb) concentration from the WW (Fabre et al. 2020). With the same starting concentration (1 mol/dm3), this efficiency was attained after 72 hours.

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Chlorella pyrenoidosa demonstrated efficient biodegradation of ceftazidime at 92.7% elimination capacity in terms of PhAC removal (Yu et al. 2017). Utilising an early algal level of 40 mg/L, this effectiveness was attained after contact duration of 24 hours. Chlamydomonas sp. was used to digest ciprofloxacin with 100% efficiency (Xie et al. 2020). The sorption process may be used to determine how well PhACs biodegrade under these circumstances. The removal of PhACs occurs in three stages: (i) fast adsorption between the cell wall and contaminants through a passive physicochemical adsorption method; (ii) cell surface trafficking of the cell wall, which takes time; and (iii) the final phases of biodegradation, bioaccumulation or both (Hena et al. 2021). Elimination rate shows that live algae are more adapted to remove organic and PhAC pollution than dyes and heavy metals.

3.3

Advanced Oxidation Processes (AOPs)

Since the costs are significant and there are practical problems, the employment of conventional procedures is not entirely acceptable in modern society. Therefore, it is essential to implement contemporary systems, such as advanced oxidative processes (AOPs) (Garrido-cardenas and Agüera 2020). The following are some of the AOPs’ characteristics: (1) potential for the oxidation of inorganic chemicals and ions of nitrates, chlorides and other pollutants, as well as the conversion of organic pollutants to CO2 and H2O, and (2) it is especially preferable to prevent the existence of potentially harmful by-products from the principal pollutants that may be produced by other procedures that do not include a biological system. Non-selective reactivity with the overwhelming majority of organic substances is particularly desired in this regard (Cuerda-Correa et al. 2020). Some of the AOPs are described as follows:

3.3.1

Catalysts Involved in Advanced Oxidation Processes (AOPs)

Both homogeneous and heterogeneous catalysts have been employed effectively in AOPs. Lack of a subsequent treatment to remove dissolved metals from the treated water, simplicity of separation of the catalyst for reuse and endurance of harsh working conditions are all obvious advantages heterogeneous systems have over homogeneous systems. Additionally, the system is efficient over a wider pH range, which includes the typical pH of drinking as well as sewage water which is at pH 2 to 9 (Kurian 2021). The AOPs, which are used to purify water, operate at pressure and temperature that are similar to those found in the environment. They entail the production of enough hydroxyl radicals to interact with the medium’s organic molecules. The best powerful oxidants are hydroxyl radicals because they satisfy a number of requirements, such as the following: (1) they do not produce more waste, (2) they are non-toxic in nature and have a short lifespan, (3) they do not corrode equipment and (4) they are typically made by simple assemblies (Garcia-Segura et al. 2012). Some

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of the most popular methods utilised for this goal include the following: various photocatalyst combinations, including UV, UV/Fe3+, UV/H2O2, UV/O3, UV/H2O2/ Fe3+, UV/TiO2, UV/S2O82- and UV/chlorine. The primary problem is how effectively the UV AOPs remove particular target pollutants. The molecular structure of the pollutants affects the rates of UV AOP removal, referring to both direct photolysis and radial reactions. Additionally, removal rates are significantly impacted by water matrix effects. For the best AOP management, each UV AOP system needs to be uniquely managed according to its water matrix and the removal of certain pollutants (Wols and Hofman-caris 2012). According to Xiang et al. (2018), the UV/chlorine oxidation method performs better than UV alone or chlorination in the majority of cases. Hydroxyl and Cl radicals were created during the UV/chlorine reaction, with the hydroxyl radical playing a leading role in the oxidation process. It contributed 28.95% control to the rate of diuron decomposition, according to the calculation.

3.3.2

Photo-Fenton Oxidation

In most AOPs, a combination of oxidants and radiation (O3/H2O2/UV) or a catalyst and radiation (Fe2+/H2O2; UV/TiO2) is used to accomplish their goals. Depending on the AOP, different drawbacks make them economically unappealing. These drawbacks include the following: (1) significant demand for electricity (for instance, ozone and UV-based AOPs), (2) high ozone, hydrogen peroxide and iron-based AOPs are only a few examples of oxidants and/or catalysts that have quite high volumes and (3) operating conditions for pH, such as Fenton and photo-Fenton, are another factor (Klamerth et al. 2010). An effective oxidation technique for treating these WWs has been found as the photo-Fenton oxidation system. Hydroxyl radicals are often produced in Fenton and Fenton-like reactions from H2O2 catalysed by iron (Fe2+, Fe2O3, Fe3O4, H2Fe2O4, etc.) (Ma et al. 2021). However, one of the main issues is the cost-effectiveness. However, using solar energy, chelating agents, heterogeneous catalysts and integrating biological treatment technologies can lower prices (Pouran et al. 2015).

3.3.3

Electrochemical Oxidation Process

Due to their cheap cost and great efficiency, electrochemical oxidation procedures among the several AOPs are becoming more and more popular for the purification of water and WW. In electrochemical oxidation processes, dissolved organic pollutants are largely oxidised by (i) charge transfer that causes direct anodic oxidation on the anode surface and (ii) interaction with physi- and/or chemisorbed hydroxyl radical generated during water oxidation (Gurung et al. 2018). The complete degradation of OMPs has been extensively investigated using electrochemical AOPs. Due to the fact that the electrochemical oxidation uses just electric current and does not need any chemicals, it is a practical and ecologically beneficial method. The first kind is

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called direct oxidation, and it takes place when a substance reacts directly at the anode’s surface, or when it reacts with physisorbed or chemisorbed •OH. The second process, indirect oxidation, produces a mediator in the bulk solution electrochemically, such as ozone (O3), hydrogen peroxide (H2O2), active chlorine, active bromine or S2O82-, among others (García-espinoza and Mijaylova 2019). Recently, coupling strategies that involve an electrochemical pre-treatment followed by a biological process have been suggested as dependable and affordable solutions to address the mineralisation of persistent compounds. The pre-treatment now aims to increase the biodegradability of non-biodegradable species rather than totally mineralise them by concentrating on functional groups that have been found to decrease biodegradability. This allows for more focused electrochemical techniques compared to those that use hydroxyl radicals (Geneste 2018).

3.4

Degradation of OMPs via Nanotechnology

Micropollutants cannot be removed using the infrastructure and traditional WW treatment techniques now in use. As a result of their shortcomings, there is a need for contemporary techniques to eliminate the residues of growing micropollutants including EDCs, pharmaceutically active compounds (PhACs), personal care products (PCPs) and pesticides. Due to the accessibility of sustainable, affordable raw materials, particularly plant extracts, in recent years, the use of nanomaterials for the reduction of water micropollutants has grown in popularity. This section addresses the use of nanoparticles in removing micropollutants from WW streams. In the literature, it has been described how to use metallic nanoparticles to remove pesticides, dyes, PCPs, heavy metals and PhACs (antibiotics) from WW. Adsorption is preferred for removal due to its sustainability and variety of adsorbents.

3.4.1

PhAC Removal

Nanomaterial adsorbents have been employed to eradicate trace levels of antibiotics (Malakootian et al. 2019). Antibiotics such as ampicillin, rifampicin, tetracycline, piperacillin, tazobactam, sulfamethoxazole, trimethoprim and erythromycin have been reported to be effectively removed by magnetite nanoparticles (Fe3O4) (Stan et al. 2017; Wanakai et al. 2022). With a percentage removal effectiveness of 97.4% and 77.3% from synthetic and actual water, respectively, green synthesised manganese nanoparticles were effectively used to remove antibiotics like mitoxantrone (MTX) from WW (He et al. 2021). The approach was described as being more affordable and having more adsorptive capacity in the same study. With a removal effectiveness of 99.2% and 99.6% for concentrations of 50 and 400 g/ml, respectively, utilising a mixture of graphene oxide and zinc oxide nanoparticles, levofloxacin was eliminated (El-Maraghy et al. 2020). Another work utilising zerovalent copper nanoparticles demonstrated clearance efficiencies

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of lactam antibiotics, cefadroxil and ceftriaxone of above 85% (Oliveira et al. 2018). Using Ni/TiO2-P25, Au/TiO2-P25 and Ag/TiO2-P25Cu/TiO2-P25 nanoparticles, photodegradation of trimethoprim was accomplished with an 80% decrease of the original concentration (Oros-Ruiz et al. 2013).

3.4.2

Pesticide Removal

In the past, researchers have looked at using nanoparticles to remove pesticides from drinking water, agricultural effluents and WW. According to Hesni (2020) and Moradi Dehaghi et al. (2014), graphene, a carbon-based nanoparticle, has an adsorption capability that ranges from 600 to 200 mg/g of pesticides. In other studies, silica-modified graphene was found to enhance the adsorption of organophosphorus insecticides in water (Liu et al. 2013). In order to remove pesticides, graphene, a carbon-based nanoparticle, was utilised, and due to their high adsorption capability, metal nanocrystalline oxides such as those found in magnesium, cerium and titanium oxides were used to remove pesticides. Nanocrystalline cerium (IV) oxide was used to facilitate the degradation of leftover organophosphate parathion methyl insecticide to less harmful compounds at favourable temperature ranges (Tolasz et al. 2020). Das et al. (2017) reported 95% chlorpyrifos degradation with the aid of laccase immobilised on iron magnetic nanoparticles. Due to the associated costs, only a limited amount of organophosphorus pesticides can be removed and destroyed using nanocrystalline metal oxides (Saleh et al. 2020). It is consequently vital to develop more types of nanomaterials to regulate pesticide contamination of the environment.

3.4.3

Heavy Metal Removal

In order to remove heavy metal ions from aqueous medium, Liu et al. (2019a, b) and Yang et al. (2019) claim that nanomaterials are a potential method. Some of the nanomaterials used to eliminate heavy metals from WWs involve zero-valent metal, nanocomposites and metal oxide-based and carbon-based nanomaterials. Lead (II) ions were removed with an efficacy of 492.4 mg g-1 by the synthesis and application of magnetic nanocomposites on aluminium metal-organic framework (Ricco et al. 2015). Carbon nanotubes (CNTs) and materials based on graphene have been utilised to eradicate heavy metals in water among carbon-based nanomaterials. By chemically interacting with the metal ions and functional groups like hydroxyl and carboxylic groups on their surface, the CNTs are able to remove heavy metals (Gupta et al. 2016). Even though CNTs are good in removing heavy metals, their usage in commercial applications is constrained by their high cost. Additionally, CNTs produce by-products that might be hazardous and their removal is more expensive. Heavy metal ions have been remediated from WW with the aid of graphene nanoparticles. Graphene oxide has been used to remove lead (II), mercury (II) and cadmium (II) with removal efficiencies of 602, 374, and 181 mg g-1,

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respectively (Yang et al. 2019). Research investigations demonstrate that heavy metal removal is accomplished using nanoparticles based on silica. According to research by Kong et al. (2014), functionalised silica nanospheres may be removed copper (II) ions from aqueous solutions of water.

3.5

Nanofibers

Nanofibers have been found to be particularly highly successful in the one-time eradication of OMPs. On the other hand, these adsorbents show flexibility in the collection of contaminants (Anjum et al. 2019). Utilising fibre layers with various pore topologies and surface chemistry may be studied in order to produce selectivity for a specific chemical. The addition of any new types of materials must take into account the adsorbent materials’ production, and operation is inexpensive since adsorption is a commonly utilised water treatment method (Ligneris 2018). Success has also been achieved with electro-catalysts built only of chemically and physically stable carbon-based materials (without requiring metals) (Liu et al. 2019a, b). For the treatment of OMPs, inexpensive, non-noble transition metals or their oxides supported in carbon nanotubes have been described. An effective solution for treating OMPs containing WW has been shown to be boron-doped diamond (Lan et al. 2017), copper-reduced graphene oxide electrode (Kumar et al. 2020a, b), copper-based nanocomposites (Kallawar et al. 2021) and boron-doped diamond with varying boron and substrate silicon or niobium contents (Wohlmuth da Silva et al. 2019).

4 Conclusions and Recommendations Organic micropollutants (OMPs) are becoming more widely recognised as a significant class of new contaminants. Due to their low environmental concentrations, these compounds are omnipresent yet practically never draw attention to themselves. The main justification for this contemporary perspective is the level of complexity required for these substances to be detected at such low quantities in analytical procedures. Analytical techniques such as gas chromatography (GC), liquid chromatography (LC) combined with mass spectrometry (MS) and high-resolution mass spectrometry (HRMS) are widely used in these detection procedures to identify and quantify OMPs present in water. As a result, it is now known that many wealthy nations’ once-regarded as clean and green environments are really polluted by OMPs. Microbe-mediated remediation of OMPs has been identified as a sustainable approach. Several emergent techniques like AOPs and nanomaterial-based remediation techniques are also effectively applied for the OMP removal from the wastewater. Based on the physicochemical properties of the contaminants, an advanced treatment must be selected.

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• Nano-based technologies have transformed the area of WW treatment due to the unique properties of nanomaterials, which are ideal for a wide range of environmental applications. • Industry, research specialists and governments must work together to find a practical solution to the problems posed by OMP methods in order to overcome the adverse effects.

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based RuO2–IrO2–TiO2 mixed metal oxide electrode. Chem Pap 75:681–690. https://doi.org/ 10.1007/s11696-020-01243-w Wohlmuth da Silva S, Matos do Prado J, Arenhart Heberle AN, Bernardes AM (2019) Electrochemical advanced oxidation of atenolol at Nb/BDD thin film anode. J Electroanal Chem 844: 27–33. https://doi.org/10.1016/j.jelechem.2019.05.011 Wols BA, Hofman-caris CHM (2012) Review of photochemical reaction constants of organic micropollutants required for UV advanced oxidation processes in water. Water Res 46:2815– 2827. https://doi.org/10.1016/j.watres.2012.03.036 Xiang H, Gao N, Lu X, An N, Tan C, Zheng Z (2018) Degradation of diuron by chlorination and UV/chlorine process: Degradation kinetics and the formation of disinfection by-products. Sep Purif Technol 202:365–372. https://doi.org/10.1016/j.seppur.2018.03.073 Xie P, Chen C, Zhang C, Su G, Ren N, Ho SH (2020) Revealing the role of adsorption in ciprofloxacin and sulfadiazine elimination routes in microalgae. Water Res 172:115475. https://doi.org/10.1016/j.watres.2020.115475 Yang J, Hou B, Wang J, Tian B, Bi J, Wang N, Li X, Huang X (2019) Nanomaterials for the removal of heavy metals from wastewater. Nano 9:424. https://doi.org/10.3390/NANO9030424 Yaseen DA, Scholz M (2019) Textile dye wastewater characteristics and constituents of synthetic effluents: a critical review. Int J Environ Sci Technol 16:1193–1226. https://doi.org/10.1007/ s13762-018-2130-z Yu Y, Zhou Y, Wang Z, Torres OL, Guo R, Chen J (2017) Investigation of the removal mechanism of antibiotic ceftazidime by green algae and subsequent microbic impact assessment. Sci Rep 7: 4168. https://doi.org/10.1038/s41598-017-04128-3

Assessment, Obstacles, and Risk Communication for Organic Micropollutants in the Urban Water Jaskiran Kaur

Abstract Industries, despite of playing an imperative role in economic development all around the world, are also considered to be the major pollutant sources as they emit an incredible quantity of organic micropollutants into the environment. Ranging from pharmaceuticals, hormones, pesticides, and plasticizers to personal care products (PCPs), several organic micropollutants are discharged into water although in quantities as small as micrograms but their effect on the aquatic ecosystem and terrestrial environment is beyond control. This eventually raises issues regarding drinking water purity and human health. Though various remediation and treatment technologies are introduced in recent years for the abatement of organic micropollutants, it is observed sometimes that the transformation products prove to be more toxic as compared to parent micropollutants. In this chapter, the possible types and updated sources of organic pollutants are discussed in light of the urban water cycle. Apart from that, light is also shed on the impacts of organic micropollutants on the biotic as well as abiotic components of the ecosystem. The potential bottlenecks of available treatment technologies are also explained in an explanatory manner. Keywords Drinking water purity · Human health · Organic micropollutants · Pesticides · Remediation technologies

1 Introduction Notwithstanding that the green revolution, urbanization, and industrialization are instrumental in the economic development of a country, the unintended ramifications it causes are a soaring concern in recent decades. In the era of the green revolution, the use of pesticides in the agriculture sector has been markedly boosted. Among the South Asian countries, India stands third in pesticide consumption (Narayanan et al. 2016). An average of 58,160 tonnes of pesticide utilization is recorded in 2018

J. Kaur (✉) Department of Biotechnology, DAV University, Jalandhar, India, Punjab © The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 R. Bhadouria et al. (eds.), Organic Micropollutants in Aquatic and Terrestrial Environments, https://doi.org/10.1007/978-3-031-48977-8_9

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(Nayak and Solanki 2021). Similarly, industrial development and urbanization are prominent in the release of certain contaminants like pharmaceuticals, heavy metals, personal care products (PCPs), flame retardants, bisphenols, etc. As per the survey by Li et al. (2023), about 20,348 kilotonnes (kt) of short-chain chlorinated paraffin have been released worldwide since 2020. The majority of these chemicals and substances belonged to the category of organic micropollutants. The term organic micropollutants is indicative of a broad array of chemicals including fertilizers, pesticides, pharmaceuticals, PCPs, herbicides, hormones, phthalates, flame retardants, plasticizers, artificial sweeteners, preservatives, detergents, surfactants, etc. which are discharged in the ecosystem in a very minute quantity (Ojajuni et al. 2015; Li et al. 2023). Using multitudinous natural as well as man-made resources, these chemicals are emitted into terrestrial and aquatic ecosystems without any regulation. For instance, organic micropollutants like polycyclic aromatic hydrocarbons (PAHs) and heavy metals are widespread in sediments, soil, dust, and road runoff (Takada et al. 1990; Roger et al. 1998; Krein and Schorer 2000; Murakami et al. 2003). About one-third of PAH has been contributed by urban runoff in the biosphere (Hoffman et al. 1984). Road dust via numerous sources, viz., gasoline, as well as diesel vehicle exhaust, pavement, tire, oil spill, etc., bring a plentiful number of PAHs into the water bodies (Brown et al. 1985; Boxall and Maltby 1997). Majority of the time the waste is released into the nearby surroundings in a raw form. As these organic micropollutants are biologically active, their long-term presence in the marine biome jeopardizes the life that exists there and eventually results in harm to human health. Albeit, several physical and chemical treatment processes are in use for neutralizing the toxicity of micropollutants: indeed, conventional wastewater treatment plants (WWTPs) are rather unsuitable for treating the organic micropollutants owing to their recalcitrant nature (Bolong et al. 2009; Oulton et al. 2010). Not only that, certain antibiotic resistance genes (ARGs) occurred in sewage effluent, drinking water, and surface water which is the result of the consumption of certain antimicrobial drugs by humans and animals which are difficult to be annihilated by wastewater treatment systems (Kummerer 2009; Hijosa-Valsero et al. 2011; Munir et al. 2011). Therefore, the aforementioned pollutants if stayed over for prolonged durations in the ecosystems can compromise the normal functioning and interactions of marine flora and fauna and in severe cases have taken a toll on the health of the population. As an example, about 50–2300 ng/L and 50–150 ng/L of triclosan in streams and seawater, respectively, are reported to be lethal to the green algae (Shao et al. 2019). Similarly, the consistent encounter with endocrine disrupters causes feminization in male fish and obstructs their growth. Before the repercussions caused by the organic micropollutants on the environment are exacerbated, timely management policies need to be implemented. The present chapter aims to comprehend the probable sources from which the organic micropollutants mark their entry into the aquifers along with the fate of these pollutants into the water bodies. Also, a deep understanding of the categories of micropollutants to contemplate the risks likely to be caused due to their unregulated

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discharge into the urban water cycle is discussed in this chapter. Multifarious detection approaches for organic micropollutants in the water resources are also addressed which would allow for adopting relevant management strategies to prevent its severity in the environment. Moreover, the likelihood of risks the organic micropollutants impart on the urban water cycle and its associated effects on the life existing in the water ecosystem and also indirect impacts on the human population is reviewed in the chapter. Lastly, the treatment approaches towards sustainable handling of organic micropollutants have been reviewed in an in-depth manner.

2 Sources of Organic Micropollutants Eventually, the majority of natural and synthetic organic micropollutants reach the aquatic ecosystem via diffusive entrance routes (Fig. 1). Nevertheless, the fate of OMPs is dependent upon their physicochemical properties, for example, vapor pressure, water solubility, polarity, and partitioning behavior as well as on the compartment wherein it is released (Farre et al. 2008; Corcoran et al. 2010; Metcalfe et al. 2013). The less water-soluble compounds, for instance, can exist in the environment for prolonged durations and exhibit toxic effects when compared to more water-soluble substances (Farre et al. 2008; Arslan et al. 2017). Sometimes, the transformation products of some OMPs like nonylphenols and nonylphenol ethoxylates are more persistent and toxic when compared to the parent pollutant (Boxall 2004; Jahan et al. 2008). Researchers have reported the occurrence of a wide diversity of OMPs including antibiotics, flame retardants, organochlorine pesticides, phthalate esters, and

Fig. 1 Major courses of organic micropollutant (OMP) entry into the aquatic ecosystem

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poly- and perfluoroalkyl substances (PFASs) in the surface and groundwater as well (Yan et al. 2013; Zhu et al. 2013; Zheng et al. 2017; Jin et al. 2019; Chen et al. 2019; Houtman et al. 2019). The principal basis of OMPs comprises municipal, hospital, and industrial effluents, landfill leachates, WWTPs, urban runoff, agricultural runoff, and septic tank leakages among which sewage and effluent treatment plants constitute a notable source of entry of organic micropollutants into the watercourses (Holm et al. 1995; Farre et al. 2008; Sackaria and Elango 2020). Salient evidence indicated the discharge of endocrine-disrupting compounds (EDCs), namely, PCPs, pharmaceutically active compounds, estrogen, brominated flame retardants, and alkylphenol surfactants in the rivers and lakes of Canada (Metcalfe et al. 2013). Pesticides are introduced into the groundwater and streams via quite a few non-point sources: agricultural fields’ runoff, seepage from pesticide contaminated areas, aerial spray, etc. (Stuart et al. 2012; Rajmohan et al. 2020). In the UK, for instance, metabolites of banned pesticides like atrazine, dichlorodiphenyltrichloroethane (DDT), and heptachlor are found in the groundwater and surface drinking water (Sinclair et al. 2010). Through bathing, cleaning, and showering activities from households and via retailer outlets, PCPs reach the WWTPs. The majority of contaminants in PCPs like parabens, glycol ethers, alkylphenol polyethoxylates, bisphenols, and cyclosiloxanes are hardly treated by WWTPs; as a result, they are persistently released into the surrounding water (Khalid and Abdollahi 2021). It has been estimated that around 36% of PAHs are discharged into the water via urban runoff (Hoffman et al. 1984). Moreover, road dust contributed a significant quantity of PAHs to the aquatic ecosystem (Boxall and Matlby 1997; Pengchai et al. 2005). Apart from this, the WWTPs are found to be the point sources of several OMPs in the water bodies (Kaur 2021). According to the study by Lindberg et al. (2014), about 10% of the mass load in WWTPs located in Sweden is because of the pharmaceutical-loaded hospital wastewater. Also, a total of 27 pharmaceuticals are found in the effluents generated from European WWTPs (Larsen et al. 2004). The unutilized antibiotics and wastes from hospitals after some time end up in the waterways (Arslan et al. 2017). Golovko et al. (2020) revealed the prevalence of 24 and 30 organic micropollutants in the sediment and lake water, respectively, from Lake Malaren, Sweden, of which concentrations ranging from low ng/L to 89 ng/L of lamotrigine (antiepileptic drug) in the waters of lake ecosystem and citalopram (antidepressant drug) in the sediment varying from low ng/g dry weight (dw) to 28 ng/g dw were observed. As per the survey conducted in the USA, in 2014, more than 76.9 million metformin was introduced into the tap water which is around 50% more than the limits prescribed by the Rhine River Basin Agency (Trautwein et al. 2014).

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3 Quantification of Organic Micropollutants in the Environment The organic micropollutants as and when present in the environment in minute quantities, say as low as in μg/L and ng/L levels, are likely to bring about acute toxicity in living organisms like fish, invertebrates, algae, etc. Therefore, there must be proper sampling and detection methods for OMPs so risks can be controlled beforehand.

3.1

Sampling Methods

For detecting the prevalence of OMPs in the environment, various sampling methods are in use like grab sampling, passive sampling, etc.. Out of these methods, passive sampling is an effective one as with grab sampling there are the problems of requirement of large sample size for concentrating the trace contaminants and tedious sample preparation methods. Passive sampling involves sample collection without visiting the site multiple times. Herein, the contaminant molecules from the sampled medium move towards the collecting medium, i.e., generally a passive sampler by means of Fick’s law of diffusion. The collecting medium traps the sample until the equilibrium is reached (Gorecki and Namiesnik 2002). Several different passive sampling devices such as Chemcatcher, microporous polyethylene tubes (MPT), diffusive gradients in thin films (DGT), polar organic chemical integrative sampler (POCIS), and semipermeable membrane devices (SPMDs) are in demand for monitoring organic micropollutants ranging from antibiotics, bisphenols, flame retardants, pesticides, polychlorinated biphenyls (PCBs), dioxins, etc. occurring in water. The Chemcatcher originally designed in 2000 is used to evaluate the pharmaceutical residues, pesticides, PAHs, etc. from aqueous environments. It consists of a polytetrafluoroethylene (PTFE) or polycarbonate body that can accommodate the receiving phase disk which is most of the time is C18 disk. Based on the nature of the organic micropollutants to be sampled, the receiving phase and membrane are selected. For example, the C18 disk enclosed in a low-density polyethylene membrane is suitable for monitoring nonpolar pollutants, while for analyzing trace metals, a chelating disk that is covered with a cellulose acetate membrane is used (Allan et al. 2007; Lobpreis et al. 2008; Aguilar-Martinez et al. 2009; Jacquet et al. 2014). The in situ concentrations of ionic compounds, pharmaceuticals, and bisphenols were passively sampled by DGT which was introduced in 1990. The DGT sampler encompasses a piston constructed from plastic and DGT caps and also the hydrophilic-lipophilic balance (HLB) layer, agarose gel diffusion layer, and PTFE membrane filter (Chen et al. 2018; Wang et al. 2019). The analyte or compound to be analyzed passes through the membrane filter and accumulates onto the binding agent

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which was covered with the diffusive gel (Gao et al. 2022). The binding phase varies depending upon the type of OMPs to be collected from aqueous environments, for instance, for sampling sulfamethoxazole with the value of octanol-water partition coefficient (log Kow) of 4, XAD18 agarose binding gel is used, whereas activated charcoal and titanium dioxide (TiO2) is used as a binding phase while measuring bisphenols and glyphosate, respectively (Chen et al. 2012; Zheng et al. 2015; Fauvelle et al. 2015). The SPMDs (semipermeable membrane devices) which were introduced in the year 1990 are comprised of sealed low-density polyethylene (LDPE) lay flat tube that is filled with the triglyceride triolein. SPMDs are used for collecting aquatic nonpolar organic contaminants, namely, organochlorine pesticides, furans (phthalates, triclosan), dioxins, PCBs, and PAHs, which are having log Kow value >3 (Huckins et al. 2006; Seethapathy et al. 2008). As the data collected through SPMDs is not affected by environmental stressors henceforth the SPMDs provides the exact information about the bioconcentration of hydrophobic organic contaminants in aquatic fauna’s fatty tissues (Gilli et al. 2005). The organic compounds that are polar in nature and have log Kow value less than 3 like surfactants, pharmaceutically active compounds, PCPs, polar pesticides, and flame retardants are sampled from water bodies using POCIS (Alvarez et al. 2009). Generally, two types of POCIS are available: one is pharmaceutical POCIS and the other is pesticide POCIS. The former consists of a single sorbent, while the latter comprises a mixture of three sorbents. The basic design of both configurations includes varying numbers of solid disks, i.e., sorbent packed between the two microporous Polyethersulfone (PES) membranes (Gong et al. 2018). Further, to prevent sorbent loss from the POCIS, the PES membrane is compressed between the two rings either constructed from stainless steel or some other rigid material (Gong et al. 2018).

3.2

Screening Methods

The screening procedures for monitoring OMPs are divided into three categories: (1) pre-target assessment where a specific analyte is detected, excluding the contaminants if any present in the sample; (2) post-target screening, where all the substances in the sample are found, including those that are eluted during chromatography from the columns; and (3) non-target screening which involves the detection of all the compounds that are accessible to a particular analysis method, but the emphasis is on knowing about the unknown substances rather than the pre-target or post-target solutes (Hernandez et al. 2005). So, non-target screening is the method of interest among researchers which in some cases can even trace the pathways of anthropogenic OMPs. Traditional methods for non-target screening of OMPs are done via mass spectrometry, but it is not so fruitful method, owing to the tedious sample preparation methods and the necessity of analysis and computer software systems. Nowadays, liquid chromatography-tandem mass spectrometry can evaluate

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the contaminants in the surroundings with high precision (Chusaksri et al. 2006; Krauss et al. 2010; Huynh et al. 2021). Muller et al. (2011) monitored organic trace elements in the drinking water employing a non-target screening approach through high-performance liquid chromatography-mass spectrometry (HPLC-MS) and reported 20 ng/L of the landfill pollutants, i.e., 1-adamantylamine in the drinking water. An extensive survey was conducted for the occurrence of OMPs in the raw as well as drinking water from the Swedish WWTP, and samples were examined by the UHPLC-MS/MS system (Karki et al. 2020).

3.3

In Vitro Screening Methods

In WWTPs and surface waters, EDCs might present which analytical methods fail to detect. Metcalfe et al. (2013) in addition to using analytical approaches make use of in vitro screening methods which involve assessing estrogen-mediated activity through yeast estrogenicity screening assay. The different classes of endocrinedisrupting compounds (EDCs) are active through (a) binding to the estrogen receptor and succeeding gene expression, (b) competitive interactions with the thyroid hormone transport protein, and (c) binding to peroxisome proliferator-activated receptor (PPAR) (Liu et al. 2005; Miller et al. 2009).

4 Risks to Urban Water Cycle Since the prominent mode of transportation of organic micropollutants (OMPs) is water and wind, rather than being confined to the areas of their origin, they spread across the globe and vehemently affect wildlife, aquatic life, and people. Day by day, the level of OMPs in water increases at alarming levels due to the introduction of some new products. Around 2.5 billion population all over the world survive groundwater contamination with OMPs, eventually making the population suffer severely (UNESCO 2017). India majorly depends upon this resource, as nearly 80% and 50% of the rural and urban populations, respectively, utilize untreated groundwater for household purposes (Chakraborti et al. 2011). Even surface waters are not excluded from the risks of receiving OMPs. In a study, the effluent from the German WWTP could contain around 21 ng/L and 62 ng/L of 17-β-estradiol (E2) and 17-α-ethinylestradiol (EE2), respectively, which is above the limits suggested by the European Commission which ultimately is disposed of into the surface water (Gerbersdorf et al. 2015). An accumulation of OMPs in the aquatic resources imposes striking effects on the resident flora, fauna, and microbial communities adversely. In this section, the inevitable consequences on aquatic habitats posed due to the OMPs are discussed in detail.

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Effects on Aquatic Fauna

The OMPs are detected in trace concentrations, but they are considered to be bioactive even at low levels, and hence, their presence causes short-term and also long-term effects on the organisms living in the marine environment (Table 1). For example, flame retardants, in particular, polybrominated diphenyl ether (PBDE), have a tendency for bioconcentration and bioaccumulation in aquatic animals because of their hydrophobic nature, thereby affecting their brain development as well as liver functioning (ter Schure and Larsson 2002). Reports on reproductionrelated problems are reported in the carp, medaka, turtle, and trout due to long-term exposure to estrogens. The 17-α-ethinylestradiol at a quantity between 5 and 6 ng/L resulted in impaired gonadal development in males of fathead minnow (Kidd et al. 2007). In Daphnia magna, the combination of diclofenac, carbamazepine, and ibuprofen in the concentration varied from 10 to 100 mg/L poses acute toxicity (Cleuvers 2003). On exposure to the diclofenac for 28 days, renal lesions were seen at a quantity of 5 μg/L and at 1 μg/L, and subcellular effects were observed in rainbow trout (Schlesinger 2004; Triebskorn et al. 2004).

4.2

Effects on Human Beings

The human beings through intake of aquatic fishes get exposed to OMPs. Animal studies revealed that fatty fish is contaminated with PBDEs and polybrominated biphenyls (PBBs) and when human consume such fishes, the PBDEs and PBBs enter into their bodies and impart genotoxic effects. In case of exposure to PBBs, fatigue, headache, increased sleep, and dizziness are observed, while PBDEs may cause neurodevelopmental dysfunction, liver tumors, etc. (Siddiqi et al. 2003). The drinking of water contaminated with pharmaceuticals and personal care products (PPCPs) leads to chronic human health risks, viz., the development of antibiotic resistance genes, endocrine disruption, and reproductive disorders (Khanal et al. 2006; Pruden et al. 2006).

5 Treatment Technologies Adopted for Organic Pollutants Some of the OMPs like steroid hormones, pharmaceuticals, pesticides, etc. occur in even parts per million (ppm) and parts per billion (ppb) quantities that offers a challenging situation for treatment approaches. PCPs are found to have high chemical stability and low biodegradability, so the conventional treatment methods are rather incompetent for their effective elimination from the water reservoirs. In the past decades, biocatalysts have come out as bioremediation agents. Bacteria and fungi have successfully exhibited remediation potential as they either change the

Organic micropollutant class Pharmaceuticals

Pharmaceuticals

Pharmaceuticals

Pharmaceuticals

Pharmaceuticals

Pharmaceuticals

Flame retardants

Pharmaceuticals

Pharmaceuticals

Pharmaceuticals

Pharmaceuticals

Flame retardants

Pharmaceuticals

S. no. 1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

13.

Polybrominated diphenyl ether Carbamazepine

Propranolol

17-α-ethinylestradiol

Gemfibrozil

Polybrominated diphenyl ether Ketoprofen

Diclofenac

Tetracycline

Erythromycin

Ethynylestradiol

Ethynylestradiol

Examples Fluoxetine

1–400 ng/g of wet tissue 6.25 mg/L

10 mg/L

5–6 ng/L

1 mM

1 mM

100 mg/L

0.0005–0.05 mg/ L

1 mg/L

1 mg/L

5 ng/L

100 ng/L

Concentration reported 0.006 mg/L

Adversely affects the liver, brain, gonad, stomach, and fillet of Catostomus macrocheilus Defective zebrafish embryo development due to oxidative stress

Feminization in males and impaired gonadal development and alteration in oogenesis in females of Pimephales promelas Reduction in growth and fecundity in rainbow trout

CYP2M activity inhibition in carp liver

Inhibition in growth of Lemna minor and Synechocystis by 20% and 70%, respectively Reduction in frond development in Lemna minor as well as production of abscisic acid was seen A decline in prostaglandin synthesis; increase in monocyte infiltration in the liver and mild symptoms of necrosis in the tubules of kidneys in Salmo trutta f. fario A lessened thymocyte viability and augmented necrosis were noticed in lake trout Salvelinus namaycush Disruption of CYP2M activity in the liver of carp

Vitellogenin induction (female yolk precursor) in males of Oryzias latipes Fecundity reduction in colonies of Danio rerio

Possible impacts Diminished terrestrial aggression in Thalassoma bifasciatum

Table 1 Reports on the organic micropollutants’s impacts on aquatic fauna

(continued)

Birchmeier et al. (2005) Thibaut et al. (2006) Thibaut et al. (2006) Kidd et al. (2007) Owen et al. (2007) Nilsen et al. (2014)

References Perreault et al. (2003) Scholz et al. (2004) Nash et al. (2004) Pomati et al. (2004) Pomati et al. (2004) Hoeger et al. (2005)

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Organic micropollutant class

Pesticides

Pesticides

S. no.

14.

15.

Table 1 (continued)

Diazinon

Diuron

Examples

7.97 mg/L

9.41 mg/L

Concentration reported

Promoted exchange of sister chromatid and DNA damage in zebrafish embryo

Induce cytotoxicity and genotoxicity in zebrafish embryo

Possible impacts

References Shao et al. (2019) Shao et al. (2019) Shao et al. (2019)

190 J. Kaur

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pesticides’ structure thereby reducing its toxicity or mineralize it into a less toxic product (Zawierucha and Malina 2011; Rajmohan et al. 2020). Phytoremediation is a lucrative and sustainable process for the restoration of sites contaminated with hazardous pollutants with the help of plants as well as associated microbes (Chigbo and Batty 2014; Weyens et al. 2015). While selecting the plant for phytoremediation purposes, certain attributes like rapid growth ability, high biomass, and competency with the other plants growing in the vicinity must be taken into consideration (Pilon-Smits 2005). Phytoremediation is observed to be capable of lowering the soil’s herbicides itself, hence preventing the residues of pesticides from reaching the water reservoirs (Fiore et al. 2019; Barroso et al. 2023). Several key studies showing the application of numerous plants in remediating diverse OMPs are reviewed in Table 2. Most of the phytoremediation studies are based on the cultivation of several plants in constructed wetlands for the exclusion of OMPs from the atmosphere (Matamoros et al. 2007; Toro-Velez et al. 2016; Zhang et al. 2016; Nguyen et al. 2019). Zhang et al. (2017) reported a 90% elimination of nonsteroidal anti-inflammatory drugs such as ibuprofen in the mesocosms planted with Berula erecta and Juncus effusus. The proficient removal of organic micropollutants is controlled by numerous factors. For example, the eradication of ibuprofen and iohexol is improved under the conditions of high temperature and aerobic environment (Zhang et al. 2017). Since plants are inefficient in metabolizing pollutants due to the lack of degradation enzymes, the partnership of plants and bacteria is suggested by numerous researchers (Glick 2010; Khan et al. 2013; Weyens et al. 2015). The endophytic bacteria get their nutrition and shelter from plants, while endophytes protect the plants from pollutants’ toxic effects (Rylott 2014). As the incidence of transformation products of OMPs in the aquifers is daunting, and for the countries where the source of water supply is only the groundwater, this has become a problem of special concern. In such a scenario, the Advanced Oxidation Process (AOP) proves to be a worthwhile practice as in this process there occurs formation of highly reactive hydroxyl (OH) radicals which can oxidize the OMPs (von Gunten 2018). Since, AOP employs ultraviolet light (UV) and chemical oxidants, like hydrogen peroxide (H2O2), ferrous (Fe2+), ozone (O3), etc. so it is the frequently followed method but in this, the issue of by-product formation arises and the by-product so formed is found to be chemically toxic like that of its parent compound or sometimes even more than that (Sharma et al. 2018). In adverse situations, these by-products exhibited genotoxicity and carcinogenicity. Nam et al. (2014) reported the efficient elimination of pharmaceuticals such as naproxen, sulfamethoxazole, diclofenac, etc., pesticides, for example, atrazine and 2,4dichlorophenoxyacetic acid using activated carbon filters. Such efficient elimination is attributable to the large surface area of activated carbon filters. Over time the activated carbon was replaced by biological activated carbon to overcome the difficulty of pore colonization due to the microbial growth.

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Table 2 Studies on the phytoremediation potential of diverse plants

2.

Organic micropollutant category Personal care products Pharmaceuticals

Name of the organic micropollutant Tonalide Ibuprofen

3.

Pharmaceuticals

Naproxen

4.

Pharmaceuticals

Diclofenac

5.

Pharmaceuticals

6.

Removal efficiency reported 94%

Carbamazepine

The plant used for removal Phragmites australis Phragmites australis Phragmites australis Phragmites australis Typha

82%

Pharmaceuticals

Ibuprofen

Populus nigra L.

100%

7.

Pharmaceuticals

Carbamazepine

Scirpus validus

74%

8.

Pharmaceuticals

Naproxen

Scirpus validus

98%

9.

Pharmaceuticals

Diclofenac

50%

10.

Pharmaceuticals

Sulfamethoxazole

11.

Pharmaceuticals

Diclofenac

12.

Herbicides

Terbuthylazine

Phalaris arundinacea L. var. picta L. Phalaris arundinacea L. var. picta L. Cyperus alternifolius Festuca arundinacea

13.

Herbicides

Terbuthylazine

Dactylis glomerata

73%

14.

Herbicides

Sulfentrazone

Canavalia ensiformis

65%

15.

Herbicides

Imidazolinone

Canavalia ensiformis

91%

16.

Herbicides

Imidazolinone

Glycine max

92%

17.

Herbicides

Imidazolinone

Vicia sativa

93%

S. no. 1.

99% 93% 93%

24–30%

69.3% 73%

References Avila et al. (2010) Avila et al. (2010) Avila et al. (2010) Avila et al. (2010) Dordio et al. (2011) Iori et al. (2012) Zhang et al. (2013) Zhang et al. (2013) Nowrotek et al. (2016) Nowrotek et al. (2016) Zhai et al. (2016) Buono et al. (2016) Buono et al. (2016) Mielke et al. (2020) Souto et al. (2020) Souto et al. (2020) Souto et al. (2020) (continued)

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Table 2 (continued)

S. no. 18.

Organic micropollutant category Herbicides

Name of the organic micropollutant Tebuthiuron

19.

Herbicides

Quinclorac

Canavalia ensiformis

13.4%

20.

Herbicides

Tebuthiuron

Lupinus albus

15%

21.

Herbicides

Quinclorac

Lupinus albus

10%

22.

Herbicides

Tebuthiuron

Crotalaria spectabilis

4.5%

23.

Herbicides

Quinclorac

Crotalaria spectabilis

1.7%

24.

Herbicides

Tebuthiuron

Stizolobium aterrimum

16.7%

25.

Herbicides

Quinclorac

Stizolobium aterrimum

6.2%

The plant used for removal Canavalia ensiformis

Removal efficiency reported 22.5%

References Mendes et al. (2021) Mendes et al. (2021) Mendes et al. (2021) Mendes et al. (2021) Mendes et al. (2021) Mendes et al. (2021) Mendes et al. (2021) Mendes et al. (2021)

6 Concluding Remarks Rapid industrialization and the adoption of modern agricultural practices make the way for the entry of OMPs into the freshwater and marine environment. The continuous accumulation of these pollutants in the biosphere is a serious issue as they are dangerous enough even at minute levels. Though with the treatment approaches they are degraded, sometimes the degradation products are even more noxious than the parent compounds. So, the repercussions caused due to the metabolites and transformation products of the natural OMPs need to be considered while designing an appropriate treatment approach for a particular pollutant. Limited literature exists in the area of mechanism with which different OMPs interact with the residents of aquatic ecosystems and the way they are degraded by adopting a particular technology is still in its infancy. Moreover, the role of various environmental factors needs to be studied thoroughly to evaluate the success rate of treatment strategies.

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Part IV

Treatment and Remediation Approaches for Organic Micropollutants

Organic Micropollutants in the Freshwater Ecosystem: Environmental Effects, Potential Treatments, and Limitations Asha Sharma, Foram Jadeja, Hardik Giri Gosai, and Shilpi Jain

Abstract Organic micropollutants (OMPs) are widely used the derivatives of pesticides, pharmaceuticals, personal care products, plasticizers, insulating foams, etc. which are widely used. A total of 53 micropollutants in all, including pharmaceuticals and personal care products (PPCPs such as sulfamethoxazole and ibuprofen), pesticides (like heptachlor and diazinon), and industrial chemicals (including perfluorooctanesulfonic acid and 4-nonylphenol), was found using metadata analysis. In a freshwater ecosystem, OMPs are introduced through biomedical waste, municipal waste, pharmaceutical waste, and fertilizers. The hazardous potential of OMPs is measured in terms of environmental persistence and mobility. OMPs are significant pollution agents that threaten human health and environmental matrices (air, water, soil, food, etc.). A variety of OMPs get adsorbed on nano-plastics and micro-plastics and get migrated to aquatic organisms where these pollutants desorb and get released into the digestive system of aquatic organisms. Long-term inputs of OMPs also cause bioaccumulation in aquatic systems and become an integral part of the food chain. In the last few decades, researchers have come up with various OMP removal and treatment techniques including fumigation, chemical-based oxidation, UV photolysis, membrane process, adsorption, advanced oxidation process (AOP), etc. These processes are again modified for maximum outputs. In AOPs (UV radiation oxidation) radical representatives (Cl, OH, O3) attacked micropollutants. The membrane process when applied with the reverse osmosis process is comparatively more effective. This chapter covers the detection and concentration of OMPs in a freshwater ecosystem and how these OMPs are transported to the freshwater ecosystem as well as their environmental impacts along with various treatment techniques. Keywords Contaminants · Impact · Management strategies · Source · Toxicity

A. Sharma (✉) · F. Jadeja · H. G. Gosai · S. Jain Department of Environmental Studies, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara, Gujarat, India e-mail: [email protected]; [email protected]; [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 R. Bhadouria et al. (eds.), Organic Micropollutants in Aquatic and Terrestrial Environments, https://doi.org/10.1007/978-3-031-48977-8_10

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Abbreviations APs BPA DEHP E1 NP OCPs OMPs PAH PBDE PCBs PCPs TCS TrC

Alkyl phenols Bisphenol A Di(2-ethylhexyl) phthalate Estrone Nonylphenol Organochlorine pesticides Organo-micropollutants Polycyclic aromatic hydrocarbons Polybrominated diphenyl ethers Polychlorinated biphenyls Personal care products Triclosan Triclocarban

1 Introduction The toxicity of organic micropollutants (OMPs) and other anthropogenic chemical pollutants has been highlighted through Rachel Carson’s Silent Spring in 1962. OMPs are detected in very low concentrations in aquatic ecosystems (ng/L to g/L) but are believed to pose serious environmental problems threats. As a result of their lower concentrations, OMPs are not properly specified in water quality laws (Farré et al. 2008). Globally, the functions and services provided by ecosystems have been considerably transformed by human-induced environmental changes. In developing countries, the concentration of several OMPs is extremely high in water bodies, because most of the products that release OMPs are sold without any prescription (García-Galán et al. 2010). The production of industrial, residential, and municipal wastes, as well as in agriculture, poultry, and dairy farms, severely pollutes the world’s water sources and sharply affects the availability of clean water. OMPs seem to be a developing global hazard among the numerous toxins that endanger the health of the world’s ecosystems (Ye et al. 2017; Singh et al. 2021a). OMPs are a diverse group of most biologically active man-made substances, including fluorinated surfactants, pesticides, industrial chemicals, pharmaceuticals, personal care product residues, disinfection by-products, and transformation products of the aforementioned substances (Schwarzenbach et al. 2010). Polybrominated diphenyl ethers (PBDEs), halogenated aliphatic hydrocarbons, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and organo-halogenated pesticides are just a few examples of the OMPs that have been widely identified in the environment. OMPs are a complex mixture of selected bioactive molecules, synthetic organic materials, and the transformation products of those materials. These OMPs are omnipotent, most of

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which end up in various aquatic ecosystems within a range from ng/L to mg/L, altering the water quality. They are considered “emerging contaminants” or “prospective pollutants” due to their continual emission and active biological nature despite the long persistence of initial and low degradation in the environment (Bueno et al. 2012). Groundwater, open water bodies, and soil environment pollution caused by these OMPs could have cumulative negative impacts along with intergenerational contact with aquatic species as well as harm human health by integrating into the ecosystem. Certain OMPs specifically pharmaceutical OMPs are continuously dumped in nearby water bodies, so these OMPs are pseudo-persistent (Brooks et al. 2006). When being introduced into aquatic habitats, OMPs can disseminate in various environmental compartments and enter aquatic ecosystems. The OMPs are derived from various sources and belong to a vast array of chemical classes as a result exerting a distinct biological adverse effect. Continuous increasing use of OMPs results in continual bioaccumulation and inflow of OMPs into aquatic environments (Arslan et al. 2017; Sörengård et al. 2019; Golovko et al. 2021). Few methodologies for micropollutant analysis are quite expensive, and the majority of research concentrates on the assessment of already selected specific analytes rather than the identification of all chemicals present in natural matrices. Traditional wastewater treatment plants are less effectively equipped to eliminate OMPs, resulting in relatively high OMP concentrations in aquatic bodies that receive treated wastewater (Knopp et al. 2016; Gruchlik et al. 2018). Consumption of contaminated food matrices such as vegetables, eggs, fish, meat, oils, and milk has been linked to neurotoxicity, cancer, endocrine disturbance, reproductive variations, blood cancer, undeveloped fetus, and asthma (Fernandes et al. 2019). In natural ecosystems, OMPs exist as a mixture of thousands of micropollutants, rather than an isolated chemical (Neale et al. 2015). In the toxicodynamic and toxicokinetic phase, a mixture of OMPs interacts at various endpoints (Backhaus and Faust 2012). Animals cannot metabolize antibiotics and thus excrete the parent material along with their metabolites through urine and feces. Some of the antibiotics are excreted even without any metabolic modification (Kümmerer 2009). OMPs from pharmaceutical sources enter aquatic ecosystems and get integrated into the food chains (Santos et al. 2007). Toxicity studies on mixtures show that in case components are administered at concentrations below no observable effect concentration (NOEC), or with compounds causing no effects as single substances at water solubility limit, severe combination effects may emerge (Smith et al. 2013). It is important to understand the destiny of OMPs in the environment as well as their detrimental impacts on accurate management and even the legal restriction of their acceptable amounts in the environment. This chapter highlights the fates of OMPs, including transformation mechanisms of OMPs, organism toxicity, other environmental impacts, and remediation strategies of OMPs. Additionally, this chapter will summarize the different sources of OMPs in water, as well as their impacts, sampling method, and treatment measures.

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2 Source of Organic Micropollutants (OMPs) in Freshwater Ecosystem Organic micropollutants (OMPs) enter surface water, groundwater, and drinking water resources from both point and non-point sources. OMPs include common home items, medications, chemicals, personal care items, pesticides, flame retardants, surfactants, and metallic trace elements (Golovko et al. 2021; Singh et al. 2021a). The OMPs occur both from anthropogenically and naturally produced chemical compounds that exist with other persistent pollutants. Surfactants, solvents, PCPs (personal care products), phthalate esters, pesticides, EDC (endocrinedisrupting compounds), PAHs (polycyclic aromatic hydrocarbons), BPA (bisphenol A), OCPs (organochlorine pesticides), PCBs (polychlorinated biphenyl), PBDEs (polybrominated diphenyl ethers), pharmaceutical products, and microcystins are thought to be the most frequent OMPs (Liu et al. 2013). Researchers reported that specific land use activities, including agriculture, release complex mixtures of numerous OMPs into water bodies, making it impossible to trace the source of an OMP. Effluents from wastewater treatment plants (WWTPs), industries, wastewater from domestic sources, and sewer overflows (CSO) are point sources for OMPs; these sources are responsible for OMP transport via soil surface runoff, preferential flow, interflow, atmospheric depositions, and leaching (Skelton et al. 2014). Pesticides are the most dangerous OMPs, accounting for 4.6 million tonnes per year, with 99% ending up in aquatic ecosystems, residential effluents, and surface runoff (Richter 2002). Significant amounts of pesticides sprayed are non-point sources for contamination of OMPs in aquatic systems. The primary factors for the introduction of PCPs into water bodies have been identified as sewage treatment plants, leachate from landfills, and livestock breeding areas (Liu et al. 2013). Municipal, industrial, and on-site wastewater treatment plants in some industries contribute significantly to the pollution of OMPs in aquatic habitats (Gago-Ferrero et al. 2017; Sörengård et al. 2019). Despite their harmful effects and toxicity, it is anticipated that the concentration of OMPs will continuously increase due to the increasing global population, depending on non-biodegradable potentials of the majority of OMPs. In addition, activities like shipping, oil spills, ballast water discharges, and industrial, municipal, and untreated sewage discharge introduce a variety of OMPs in aquatic habitat daily (Sánchez-Avila et al. 2010; Singh et al. 2021b). Aquatic plants mostly experience OMP toxicity from pharmaceutical wastes, but unfortunately, very less information is available on pharmaceuticals in aquatic ecosystems (Arslan et al. 2017). Furthermore, humic and fulvic acids have a higher affinity for bonding with hydrophobic OMPs, causing the water to deteriorate and become contaminated (De Paolis and Kukkonen 1997). Sediments behave as a sponge because OMPs express high water partition coefficients, trapping them and displaying high hydrophobicity as a result (Gong et al. 2012). Hydrophobic OMPs have a high binding potential for sediments in water (Yang et al. 2017). In the sediment-water system, OMPs aggregate and desorb, and the sediments gradually release the bioavailable fraction of trapped OMPs to benthic and other aquatic

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Fig. 1 Source of organic micropollutants (OMPs) in freshwater ecosystem

species (Petrie et al. 2015). Overland flow from agricultural and livestock regions is a major source of micropollutants, especially when pesticides used to promote agricultural output and hormones and antibiotics used to keep cattle healthy are considered. Figure 1 presents the source of OMPs in the freshwater ecosystem. OMPs are active pollutants in the freshwater ecosystem. In water ecosystems, OMPs are introduced through various sources, and several studies have been done to identify the range of contamination. Concentrations of the different OMPs such as DEHP [di(2-ethylhexyl) phthalate], NP (nonylphenol), BPA (bisphenol A), TCS (triclosan), estrogen, TrC (triclocarbon) from the freshwater ecosystem are mentioned in Table 1.

3 Sampling of Organic Micropollutants (OMPs) Active sampling and passive sampling are the two broad types of OMP sampling. An active sampling includes traditional methods such as grab and spot sampling, which are inefficient because OMP concentrations fluctuate frequently in aquatic ecosystems because these pollutants degrade the quality of water at a specific period and place, which changes over time due to environmental factors (Schreiner et al. 2020). Such interventions of environmental factors can be sorted through frequent sampling which is again overpriced and takes a long time (Goumenou et al. 2021). To overcome these drawbacks of active sampling, integrative passive sampling (PS) along with online monitoring came into existence. It was found that online monitoring requires expensive instrumental setups and high maintenance charges

2

Sr. no. 1

Nonylphenol (NP)

OMPs Di-(2-ethylhexyl) phthalate (DEHP)

China

Mexico

Country India

West Bengal Monterrey, Nuevo León Wuhan Nanjing Section

Uttar Pradesh

Kerala Madhya Pradesh

Chhattisgarh Delhi

Bihar

Area description Assam

Liangzi Lake Yangtze River

Doomdooma River Tea Garden, Doomdooma (groundwater) Gandak River Ganga River Kharun River Yamuna River IARI, groundwater Periyar River Seondha, Sindh River Narmada River Sone River Sarsawa Pond Ganga River Cane River Gomti River Chaurali Village, Gautam Buddha Nagar (groundwater) Achheja Village, Gautam Buddha Nagar (groundwater) Torsa River Santa Catarina River

Table 1 Concentration of organic micropollutants (OMPs) in freshwater ecosystem

0.011 ± 0.8 μg/L 0.4297 μg/L

2932.637 μg/L 60 μg/L

3383.478 μg/L

4878.161 μg/L 1440.815 μg/L 3050.504 μg/L 1170.408 μg/L 2189.174 μg/L 3563.351 μg/L 1708.018 μg/L 2760.846 μg/L 2817.806 μg/L 2626.395 μg/L 2551.365 μg/L 2951.472 μg/L 2643.072 μg/L 4263.513 μg/L

Concentration 2791.044 μg/L 4851.558 μg/L

Cruz-López et al. (2020) Xu et al. (2022) Liu et al. (2017)

Reference Saha et al. (2022)

208 A. Sharma et al.

South Africa

Morocco India

Eastern Cape Province

Uttar Pradesh

Ladakh Madhya Pradesh

Kerala West Bengal

Chhattisgarh Delhi

Bihar

Rabat Assam

Bou Regreg River Tinsukia, Doomdooma River Tea Garden, Doomdooma (groundwater) Gandak River Ganga River Thakurain Tola Village, Kharun River Yamuna River IARI, groundwater Periyar River Torsa River Ganga River Leh, Sindhu River Seondha, Sindh River Amarkantak, Narmada River Shahdol, Sone River Saharanpur, Sarsawa Pond Allahabad, Ganga River Banda, Cane River Lucknow, Gomti River Jhansi, Betwa River Bareilly, Ramganga River Chaurali Village, Gautam Buddha Nagar (groundwater) Achheja Village, Gautam Buddha Nagar (groundwater) Bloukrans River 2.55 μg/L

2.110 μg/L

21.770 μg/L 0.353 μg/L 3.046 μg/L 0.353 μg/L 1.068 μg/L 2.607 μg/L 1.061 μg/L 0.984 μg/L 0.471 μg/L 1.083 μg/L 1.132 μg/L 1.776 μg/L 1.296 μg/L 1.114 μg/L 1.160 μg/L 6.825 μg/L 1.106 μg/L 1.347 μg/L 1.961 μg/L

0.011–0.2 μg/L 1.308 μg/L 1.100 μg/L

(continued)

Farounbi and Ngqwala (2020)

Chafi et al. (2022) Saha et al. (2022)

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Sr. no. 3

OMPs Bisphenol A (BPA)

Table 1 (continued)

India

Morocco Spain

Country Mexico

Uttar Pradesh

Chhattisgarh Delhi Kerala Ladakh Madhya Pradesh

Bihar

Rajasthan Assam

Area description Monterrey, Nuevo León Rabat Portugal

61.476 μg/L 16.185 μg/L 5.775 μg/L 19.862 μg/L 27.252 μg/L 1.331 μg/L 2.440 μg/L 1.335 μg/L 6.058 μg/L 3.944 μg/L 3.500 μg/L 2.539 μg/L 12.886 μg/L 1135.925 μg/L 22.309 μg/L 324.722 μg/L

0.095–0.299 μg/L 4.487 μg/L 4.194 μg/L

0.015–0.302 μg/L 0.46–4.8 μg/L

Bou Regreg River Minho river Ahar river Doomdooma River Tea Garden, Doomdooma (groundwater) Gandak River Ganga River Kharun river Yamuna River Periyar River Sindhu River Sindh River Narmada River Sone River Sarsawa Pond Ganga River Cane River Gomti River Betwa River Ramganga River

Concentration 0.9 μg/L

Santa Catarina River

Reference Cruz-López et al. (2020) Chafi et al. (2022) Salgueiro-González et al. (2015) Williams et al. (2019) Saha et al. (2022)

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4

Triclosan (TCS)

India

South Africa

China

Kerala Ladakh Madhya Pradesh

West Bengal

Chhattisgarh Delhi

Bihar

Arkavathi river Assam Doomdooma River Tea Garden, Doomdooma (groundwater) Gandak River Ganga River Kharun river Yamuna River IARI, groundwater Torsa River Ganga River Periyar River Sindhu River Seondha, Sindh River Narmada River

Chaurali Village, Gautam Buddha Nagar (groundwater) Achheja Village, Gautam Buddha Nagar (groundwater) West Bengal Torsa River Ganga River Yangtze River, Taihu Lake, Yellow River, Songhuajiang River, Heilongjiang River, Grand Canal, Dongjiang River Eastern Cape Bloukrans River Province Torsa River

47.978 μg/L 6.326 μg/L 39.149 μg/L 26.279 μg/L 9.418 μg/L 62.124 μg/L 0.424 μg/L 5.691 μg/L 10.945 μg/L 17.840 μg/L 9.463 μg/L

1.761 μg/L 33.334 μg/L 10.107 μg/L

0.055–0.184 μg/L

0.477 μg/L

183.935 μg/L 12.791 μg/L 0.01246–1.28625 μg/ L

572.806 μg/L

(continued)

Farounbi and Ngqwala (2020) Das Sarkar et al. (2020) Gopal et al. (2021) Saha et al. (2022)

Xu et al. (2019)

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OMPs

Estrogen

Triclocarbon (TrC)

Sr. no.

5

6

Table 1 (continued)

India India

Morocco Poland Morocco Spain

Malaysia China

Country

Chhattisgarh Delhi

Ahar river Bihar

Gandak River Ganga River Kharun river Yamuna River IARI, groundwater

Sone River Uttar Pradesh Sarsawa Pond Ganga River Cane River Gomti River Ramganga River Chaurali Village, Gautam Buddha Nagar (groundwater) Achheja Village, Gautam Buddha Nagar (groundwater) Lui River, Selangor River, and Gombak River Yangtze River, Taihu Lake, Yellow River, Songhuajiang River, Heilongjiang River, Grand Canal, Dongjiang River Bou Regreg River Underground water (aquifer), Kraków city Bou Regreg river Tagus River

Area description

Chafi et al. (2022) Rusiniak et al. (2021) Chafi et al. (2022) Rico et al. (2019)

0.049–0.301 μg/L 0.005–0.0131 μg/L 0.005–0.277 μg/L