Emerging Aquatic Contaminants: One Health Framework for Risk Assessment and Remediation in the Post COVID-19 Anthropocene

By Manish Kumar

Emerging Aquatic Contaminants: One Health Framework for Risk Assessment and Remediation in the Post COVID-19 Anthropocene highlights various sources and pathways of emerging contamination, including their distribution, occurrence, and fate in the aquatic environment. The book provides detailed insight into emerging contaminants' mass flow and behavior in various spheres of the subsurface environment. Possible treatment strategies, including bioremediation and natural attenuation, are discussed. Ecotoxicity, relative environmental risk, human health risk, and current policies, guidelines, and regulations on emerging contaminants are analyzed. This book serves as a pillar for future studies, with the aim of bio-physical remediation and natural attenuation of biotic and abiotic pollution.

• Includes real-world applications and case studies to show how these practices can be adopted
• Presents global coverage, with a diverse list of contributors, all of whom are experts in the field
• Uses illustrative diagrams to provide a clear and foundational understating of the topics

• Language: English
• Publisher: Elsevier Science
• Release date: Mar 3, 2023
• ISBN: 9780323960014

Book preview

Section I

Distribution, and occurrence of emerging contaminants

1. Sampling and analysis of emerging pollutants in aquatic environment 3

2. Pharmaceutical and personal care products in the seawater: Mini review 35

3. Microplastics in aquatic and atmospheric environments: Recent advancements and future perspectives 49

4. Monitoring residues of neonicotinoid pesticides in paddy grains along the agro-ecosystems of the Cauvery delta region, South India 85

5. Emerging COVID waste and its impact on the aquatic environment in India 101

Chapter 1

Sampling and analysis of emerging pollutants in aquatic environment

Tirtha Mukherjeea, Vajinder Kumara and Sukdeb Palb,c

aDepartment of Chemistry, Akal University, Talwandi Sabo, Bathinda, Punjab, India

bWastewater Technology Division, CSIR-National Environmental Engineering Research Institute, Nagpur, Maharashtra, India

cAcademy of Scientific and Innovative Research (AcSIR), Ghaziabad, Uttar Pradesh, India

1.1 Introduction

Pollutants are not a new thing. It is our ancestral inheritance, dating back to the birth of human civilization. However, during the Second World War, there is a revolution in the chemical industry and we begin to produce more and more chemical compounds. Very quickly some of the most severe adverse effects of these compounds were felt. From around 1970 there were efforts to limit such chemicals by various regulations. One of the milestones in the antipollution movement was the Stockholm Convention on Persistent Organic Pollutants signed by 151 countries. The Convention entered into force on 17 May 2004. It lists many chemicals under the persistent chemicals category. According to this Convention, the persistent pollutants (PP) have the following properties: (a) have a long half-life in years; (b) move easily and hence get distributed widely in soil, water and air; (c) has the property of bioaccumulation; and are toxic to the biosphere (Convention). From the defining properties of this class of pollutants, it can be seen that these are the chemicals that are most easy to study. Hence, they are also most discussed academically and administratively.

Along with these persistent pollutants, another class of pollutants has gained headlines in recent times. These are called emerging pollutants (EP). An EP can be (a) a recently introduced compound that could pose a threat to the environment or (b) an old contaminant whose environmental impact is only recently discovered or (c) a known pollutant for which recent research is throwing up new environmental issues. These compounds are not currently regulated and hence not routinely monitored but they are investigated for future regulations (Dulio et al., 2018).

The ambit of EP makes them a large, diverse and fluid class of compounds. Any of the hundreds of compounds introduced yearly may be classified as EP if they are released in the environment and their detrimental effect on the environment is indicated. Any old contaminant may enter the fold of EP if new harmful effects were identified. At the same time, a contaminant may move from EP to PP in light of new experimental evidences. To date, NORMAN is the most comprehensive database for EP. It was established in 2004 by the EU Commission with the stated aim of a permanent network of reference laboratories and related organizations dealing with emerging environmental substances (Brack, 2011). According to NORMAN, there are 21 classes of EP. These are (1) biocides (BIOCID): chemical substance intended to destroy, deter, render harmless, or exert a controlling effect on any harmful organism, e.g., cyproconazole, phoxim, etc. (2) drinking water chemicals (DW): chemicals produce due to water treatment, e.g., 1,1,1,3,3-pentachloropropanone, 1,1,1,3-tetrachloropropanone, etc. (3) drugs of abuse (DOA): certain chemicals for the purpose of creating pleasurable effects on the brain, e.g., cocaine, dihydrocodeine, etc. (4) flame retardants (FRET): chemical used to make material resistance to fire, e.g., octabromodiphenyl ethers, tetrabromobisphenol A, etc. (5) food additives (FOODA): chemicals added to food to improve its quality, e.g., sucralose, triacetin, etc. (6) food contact chemicals (FOODC): chemical used in food packaging, e.g., bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate, etc. (7) human metabolites (HUME): transformed products formed by human metabolism, e.g., 2-N-glucuronide lamotrigine, 4′-hydroxydiclofenac, etc. (8) human neurotoxins (HUTOX): chemical which could be neurotoxins for human, e.g., nicotine, 4-chlorobiphenyl, etc. (9) indoor environment substances (INDOOR): pollutant which are expected to be found in indoor environment, e.g., 2-methylnaphthalene, phthalimide, etc. (10) industrial chemicals (IND): chemicals used in industry, e.g., acetaldehyde, biphenyl, etc. (11) metals and their compounds (MET): Different metals and their organometallic compounds, e.g., tetraethyl lead, tetramethyl lead, etc. (12) natural toxins (NATOX): toxic compound produce from biological source, e.g., tetrahydrocannabinol, tyramine, etc. (13) per- and polyfluoroalkyl substances (PFAS): A series of fluorinated organic compounds, e.g., perfluorobutanoic acid, perfluoropropanesulfonic acid, etc. (14) persistent, mobile and toxic substances (PMT): substance that are persistent in environment mobile in water and toxic, e.g., venlafaxine, amitriptyline, etc. (15) personal care products (PCP): chemicals used in various personal care products such as UV filters, disinfectants, fragrances, preservatives and insect repellents, e.g., N,N'-dimethylimidazolidinone, acetaminophen, etc. (16) pharmaceuticals (PHARMA): different drugs released in environment, e.g., beta-sitosterol, domperidone, etc. (17) plant protection products (PPP): chemicals used in agricultural to protect plants from weeds, diseases and pests, e.g., ametryn, fenarimol, etc. (18) plastic additives (PLAST): chemicals added to plastic to modify its properties, e.g., N-methyl-2-pyrrolidone, diethyl phthalate, etc. (19) REACH chemicals (REACH): chemicals listed in Registration, Evaluation, Authorisation and Restriction of Chemicals, e.g., 4-nitrobiphenyl, methylenediphenyl diisocyanate, etc. (20) smoke compounds (SMOKE): chemicals found in smoke, e.g., N-nitrosodimethylamine, p-xylene etc. and (21) surfactants (SURF): different surfactants, e.g., naphthalene sulfonic acid, 4-Nonylphenoxy acetic acid etc. (NORMAN,). Some of the major EPs are shown in Fig. 1.1.

Figure 1.1 Some of the major types of emerging pollutants.

EPs are produced by almost all anthropogenic activities, including agricultural, residential, and industrial operations, and are released into the environment. Fig. 1.2 shows some of the sources of EPs.

Figure 1.2 Major routes of movement of emerging pollutant in aquatic environment.

A major cause of concern is; as the data available on EPs are limited and the compounds are not generally covered under environment protection law, most wastewater treatment plants are not designed to remove EPs. In one investigation, 41 EPs were discovered in ten diverse wastewater treatment plants in a highly urbanized area of France, including 37 pharmaceutical residues (such as antidepressants, antihypertensives, or schizophrenic medications) and four pesticides. For more than half of these EPs, the median removal rates were found to be either negative or low, resulting in considerable EP concentrations in treated wastewater (Wiest et al., 2021). Another study found 35 pharmaceuticals, 15 pesticides, 13 poly-/perfluorinated alkyl substances (PFASs), 2 organophosphate flame retardants (OPFRs), 2 corrosion inhibitors, and 3 metabolites in effluents from water treatment plants in two Korean cities, Gumi and Daegu (Choi et al., 2021). Peña-Guzmán et al. (2019) reviewed the presence of EPs in the urban water cycles of South America. Zhou et al. (2019) detected 284 pharmaceuticals compounds in one or more of 33 European countries. Anti-inflammatory drugs (diclofenac and acetaminophen), hypertensive drugs (irbesartan and valsartan), a stimulant (caffeine), an artificial sweetener (acesulfame), and a corrosion inhibitor (2-hydroxybenzothiazole) were found to be the most common in three Basque estuaries, according to another study (Mijangos et al., 2018). Not only water there is numerous reports of penetration of these EPs in fauna and flora. For example, perfluorodecanoic acid, perfluorononanoic acid, perfluoroheptanoic acid, and diclofenac were detected in the concentration ranges of 20.13–179.2 ng/g, 21.22–114.0 ng/g, 40.06–138.3 ng/g, and 551.8–1812 ng/g, respectively in the small and medium-sized pelagic fish species (Thyrsitesatun (snoek), Sarda orientalis (bonito), Pachymetoponblochii (panga), and Pterogymnuslaniarius (hottentot)) obtained from Kalk Bay harbor, Cape Town (Ojemaye and Petrik, 2019).

Once in the environment, these EPs can be biotransform into other metabolites; and frankly speaking, we know very little about these transformations (Dey et al., 2019). Some of these metabolites may be more toxic than the parent compounds. Also, their effect on the nontargeted organism is scarcely understood. Though, already available reports are a cause of concern. Carbamazepine and diclofenac, for example, have been found to harm algal chloroplasts in aquatic environments (Vannini et al., 2011). Sulfamethoxazole exposure over time causes significant toxicity and inhibits photosynthesis (Liu et al., 2011). There were reports of bioaccumulation of EPs in Indo-Pacific humpback dolphins (Sousa chinensis). This dolphin leaves in shallow water near the coast and is thus especially vulnerable to anthropogenic activities (Sanganyado et al., 2018). Reproduction damage was reported in medaka fish (Oryziaslatipes) at the environmentally relevant concentration range of ibuprofen (Han et al., 2010). The list of similar papers can go on.

The first step toward understanding the incidence and fate of EP requires its quantification in many environmental compartments. This is not an easy feat. The job is complicated from the start by the number and diversity of EPs. Not helping, is the fact that their importance shifts over time as a result of changes in chemical production, usage, and disposal, as well as new understanding of their incidence, fate, and risks. Furthermore may EPs such as organophosphorus insecticides, pyrethroids, and hormones affect the aquatic environment at extremely low concentration limits (Geissen et al., 2015). Thus, the proposed analytical method must be up to the task. Table 1.1 summarized some of the recent reports of EP analysis.

Table 1.1

There are many excellent reviews available on the subject. They are mainly of two types: reviews on specific techniques and reviews on the specific type of emerging pollutant. An example of the first type is the recent article by Sivaranjanee et al. (2022) where they reviewed different electrochemical systems for sensing emerging contaminants in aquatic environments. Ricciardi et al. (2021) on the other hand review specific emerging pollutant microplastics. Another review set takes a holistic view of the subject and discusses the sampling and analysis accepted in the context of the occurrence and fate of emerging pollutants in the aquatic environment (Vasilachi et al., 2021). However, there is a shortage of literature summing up all the current development in sampling and analytical techniques without being biased on any one technique or any one type of pollutant. The current chapter summarized the latest sampling and analysis techniques used to detect and monitor the EPs in the aquatic environment. This chapter hopes to give a bird's-eye view of the matters without giving extensive details; for which extensive reviews are available. The target reader for the chapters is new researchers who will gain primary knowledge about all the tools available in the field as well the precautions they must exercise.

1.2 Sampling

Sampling is the first step in any environmental analysis and monitoring program. It is also the most crucial step. An improper sampling technique will induce an insurmountable bias in the analysis. The sample should be a true representative of the original matrix. It should be free from any contamination or modification arising from the collection, transportation and storage process employed before analysis. This is especially challenging for EPs as the biotransformation and mutual interaction of many compounds classified under EP are poorly understood.

A successful sampling starts from the proper planning and training of the personnel. The next stage is the collection of samples from the field, their packaging and transport; according to the planned strategy. Aliquoting the collected sample is the final but sometimes forgotten step of the procedure, especially if the collected sample is inhomogeneous or there is a possibility of change in the sample matrix in the laboratory environment.

A successful sampling plan should include (1) a sampling objective (2) a sampling method that will give a proper representation of the matrix, (3) the sample quantity that will fulfill the minimum sample requirement of the analysis techniques, (4) possible quality control measure that will quickly identify defective samples, (4) assessment of safety issues during sampling and (5) safety protocol to ensure a safe sampling (Kot et al., 2000; Madrid and Zayas, 2007).

The sampling techniques can be boldly classified into two categories; (a) traditional sampling and (b) passive Sampling Techniques. Traditional sampling also called active sampling involve require physical intervention or energy input to collect or extract sample. In contrast passive sampling relies on free flow of analyte molecules from the sample medium to a receiving phase on account of difference in chemical potential. The major difference including advantage and disadvantages of both sampling method are list in Table 1.2.

Table 1.2

1.2.1 Traditional sampling techniques

Traditional sampling or active sampling allows the researcher to determine the time and location of the sampling. Because aquatic environments are subject to seasonal fluctuations, multiple samples spanning different seasons may be required to record the time average value or seasonal variation in pollutant concentrations. Traditional sampling techniques give the researcher better control, allowing them to capture special or temporal fluctuations in the pollutant concentration. At the same time, it is more prone to sampling errors. Because the sample collected is not a time or space averaged but depends on the discretion of the researcher.

The world's water reserve can be divided into two major categories: (a) surface and (b) groundwater. The third important type of water matrix is pore water found in sediment: a natural deposit of rocks, sand, and silt in contact with the water body or Sludge: a semisolid residual material of water treatment plants.

For sampling purposes, surface water is divided into two categories: flowing and stationary. If the flow rate of water is higher than approximate 0.5 m/s then an isokinetic sampling must be used (Wilde and Radtke, 1998, Chap. 4). In isokinetic sampling, water enters the sampler at the same rate it is flowing. For all other cases nonisokinetic samplers were used. The simplest nonisokinetic technique is to submerge laboratory cleaned bottle in the water. A dipper or pond sampler can be used instead of bottle. It had a handle attached to the sampling beaker. Weighted bottle samplers are suitable for collecting samples from a particular depth. They have an attached weight that keeps the collecting vessel upright. The cap of the container can be opened remotely once the sampler reached the required depth. More sophisticated instruments were available to collect the discrete sample from a specific spot. These are VanDorn Sampler, Niskin Bottle Sampler, Double Check Valve Bailers and Churn Splitter. If volatile organic compounds (VOC) were to be analyzed then a special sampler designed for the purpose must be used. There are also autosamplers that can collect samples remotely.

The main challenge in collecting pore water samples is to isolate the water from the solid particles. Pore waters are normally extracted in the laboratory from the collected sediments or slugs by centrifugation or pressure extraction. If they are extracted in sampling site, they are acquired via several physical techniques such as squeezing, centrifugation, vacuum suction. Sediment probes are a special type of sampler which is used for collecting pore samples. They contain a porous disc of ceramic or plastic attached to a syringe. Water can be collected into the container through the porous disc by operating the syringe manually or through an automated vacuum pump (Raza et al., 2018).

Groundwater is generally much more homogeneous than surface water hence its sampling is much easier. Samples are normally collected from supply wells or monitoring wells. The most important challenge here is to ensure that the sample is not contaminated from the supply line.

For all these various samples the choice of proper preservation is very important. The most frequently used preservative technique for EP is storing at 4°C and/or using H2SO4 to bringing the pH below 2 (Vaz, 2018).

Whatever sampler is used the following points must be considered:

(1) Sampling must create minimum turbulence; especially it must not disturb the sedimentation.

(2) If the sample is to be transferred from a collecting device, then the device must not come in contact with the final storage container.

(3) Considering the nature of the analyte and the composition of the sample matrix proper ullage must be decided and maintained. For example, for the determination of VOC, there should not be any ullage.

(4) All samples requiring preservation must be preserved as quickly as possible. The efficiency of the preservative must be checked and if found inadequate more preservatives must be added.

1.2.2 Passive sampling techniques

Passive sampling is a time-integrated sampling technique. Here samples are collected over an extended period of time (Nitti et al., 2022). Hence, it is not affected by the fluctuations in the sampling matrix. It is also effective in detecting episodic changes in EP, missed by the traditional method (Górecki and Namieśnik, 2002). An episodic change is an infrequent discontinuous change in the concentration of the pollutant. The timing and maximum concentration of such events are unknown. The volume of the collected samples is 10–100 times larger than the traditional sampling. This increases the sensitivity and detection limit of the analysis (Kot-Wasik et al., 2007).

Passive sampling involves the movement of pollutants from the bulk phase (sample medium) to the receiving phase in the sampler. The movement is facilitated only by the difference in chemical potential between the phases (Namieśnik et al., 2005). The transfer will continue till the chemical potential of the analyte in both phases become equal that is equilibrium is reached. Both uptake and elimination of analyte in the receiving phase generally follow fast order kinetics. At the start of sampling, the rate of elimination is negligible compared to the rate of uptake. Thus, at the initial stage, the uptake of analyte in the receiving phase is linear with the exposure time. As the analyte accumulates in the receiving phase the rate of elimination increases and after a time (tk) the rate of accumulation is no longer linear but follows a curve path ultimately reaching an asymptote at the equilibrium (Vrana et al., 2005). A sampler that operates at the liner phase is called a kinetic passive sampler. The equilibrium passive sampler on the other hand operates at the equilibrium condition (Fig. 1.3) (Taylor et al., 2021).

Figure 1.3 Kinetics of passive sampler.

Many different types of special samplers are employed for the analysis of EPs. A semipermeable membrane device (SPMD) involves a thin film of liquid receiving phase encased in a nonporous polymer such as low-density polyethene (Fig. 1.4). Natural lipids such as triolein are most frequently used in receiving phase (Huckins et al., 1993). As both the membrane and the liquid lipids are hydrophobic these devices are especially suitable for analytes that have octanol-to-water partition coefficients greater than 3. More polar analytes are generally sampled in polar organic chemical integrative samplers (POCIS) (Fig. 1.5). In POCIS a polar absorbent is encapsulated in hydrophilic microporous membranes made of materials such as polyethersulfone (Godlewska et al., 2020).

Figure 1.4 Schematic representation SPDM sampler.

Figure 1.5 Schematic representation of polar organic chemical integrative sampler (POCIS).

The diffusive gradient in thin-film (DGT) was developed for sampling inorganic ions. At the core of the DGT device is a gel embedded with a binding element which acts as the receiving phase (Fig. 1.6). The innovative part of this device is a diffusion gel which separates it from the main body of water. This gel is generally made from hydrated acrylamide. This layer limits the mass transfer of analyte during sampling to diffusion within this layer. The sampling rate is thus determined by the rate of this rate limiting diffusion step. Hence the influence of environmental conditions on the sampling rate is minimum in this device. Thus, it is easier to time-weighted average concentration from the analyte concentration in the receiver phase. DGT devises for sampling organic analytes were also reported, these devices are called o-DGT and they basically have a different binding component to receive the targeted organic molecules (Guibal et al., 2019).

Figure 1.6 Schematic representation of diffusive gradient in thin-film (DGT) sampler.

Chemcatcher® also uses a diffusion layer for the same purpose but here the receiving phase is solid (Fig. 1.7). Both the phases are supports and seals in inert polymer housing. Chemcatchers are available for a range of EP. They use various combinations of diffusion and receiving phase. For example for nonpolar organic molecules C18 Empore disk receiving phase and low density polyethylene diffusion phase is most popular for polar organic molecules however polyethersulfone diffusion phase is used with C18 Empore disk receiving phase. For metal ion a chelating extraction disk is used as receiving phase in combination with cellulose acetate diffusion phase (Vrana et al., 2005).

Figure 1.7 Schematic representation of Chemcatchers sampler.

All these different passive samplers have a common design. They have two most important components. A receiver phase where the analyte will be collected and a barrier which separates the receiver phase from the sampled matrix. These barriers regulate the movement of analyte form the sampled medium to the receiver phase. Barriers are of two types: (1) barriers that works on diffusion such as those found in DGT or chemcatcher and (2) barriers that works on permeation such as those found in SPMD or POICIS. Once exposed to water the targeted analyte reaches the receiver phase through the barrier and get accumulated their due to higher affinity of the receiver phase toward the analyte. This helps in determine analytes which are present in very low concentration in aqueous phase. There must be a quantitative relationship between the analyte accumulated in the receiver phase and the analyte concentration in water. The sampling time depends on the type of the sampler (kinetic or equilibrium) design of the sampler, the nature of the barrier and receiving phase and environmental variables such as water temperature turbulence and fouling. The last factor is difficult to control and reproduce hence the sampler designed with the aim to minimize this effect.

Design wise the samplers are of two types. Tube shape samplers have a low ratio of receiving phase surface area to stagnated sampled media area, which acts as the diffusion or permeation phase. These types of designs are good to eliminate the effect of environmental variables. However due to small surface area of the receiving phase this sampler are less sensitive. Badge-type samplers have a higher surface area of receiving phase and smaller area of the diffusion phase. This improves sensitivity. The problem of the effect of environmental variables is minimized by the addition of a separated immobilized diffusion phase.

After the predetermined expose time the passive samplers are collected. The analytes are extracted from the receiver phase and their concentrations are determined. A calibration is then needed to correlate the analyte concentration in the receiver phase to that in the sampled medium. For equilibrium sampler distribution constants are available in the literature or it can be determined with relative ease in the laboratory. Determining absorption kinetics for kinetic sampler is more difficult. Calibration curves are usually prepared in the laboratory after extensive kinetic studies with known analyte concentrations under different conditions (Vrana et al.,