Environmental Research 207 (2022) 112609

Contents lists available at ScienceDirect

Environmental Research
journal homepage: www.elsevier.com/locate/envres

Emerging contaminants of high concern for the environment: Current

trends and future research
Shamshad Khan a, **, Mu. Naushad b, *, Muthusamy Govarthanan c, Jibran Iqbal d,
Sulaiman M. Alfadul e
a
School of Geography and Resources Science, Neijiang Normal University, Neijiang, 641100, China
b
Advanced Materials Research Chair, Department of Chemistry, College of Science, King Saud University, Riyadh, 11451, Saudi Arabia
c
Department of Environmental Engineering, Kyungpook National University, Daegu, 41566, Republic of Korea
d
College of Natural and Health Sciences, Zayed University, P.O. Box 144534, Abu Dhabi, United Arab Emirates
e
King Abdulaziz City for Science and Technology, Riyadh, 11442, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: Wastewater is contaminated water that must be treated before it may be transferred into other rivers and lakes in
Emerging contaminants order to prevent further groundwater pollution. Over the last decade, research has been conducted on a wide
Removal techniques variety of contaminants, but the emerging contaminants are those caused primarily by micropollutants, endo­
Environmental pollution
crine disruptors (EDs), pesticides, pharmaceuticals, hormones, and toxins, as well as industrially-related syn­
Wastewater
thetic dyes and dye-containing hazardous pollutants. Most emerging pollutants did not have established
guidelines, but even at low concentrations they could have harmful effects on humans and aquatic organisms. In
order to combat the above ecological threats, huge efforts have been done with a view to boosting the effec­
tiveness of remediation procedures or developing new techniques for the detection, quantification and efficiency
of the samples. The increase of interest in biotechnology and environmental engineering gives an opportunity for
the development of more innovative ways to water treatment remediation. The purpose of this article is to
provide an overview of emerging sources of contaminants, detection technologies, and treatment strategies. The
goal of this review is to evaluate adsorption as a method for treating emerging pollutants, as well as sophisticated
and cost-effective approaches for treating emerging contaminants.

1. Introduction cosmetics, insecticides, personal care products medicines, and steroid

hormones (Houtman, 2010; Khan et al., 2018a; Luo et al., 2014). The
The major environmental problem has increased dramatically worldwide output of these pollutants is predicted to have increased from
because of the high quality of life and the requirement of consumers. 1 million to 500 million tons each year (Thomaidis et al., 2012). How­
There are numerous environmental hazards, such as toxic waste ever, these natural or manufactured compounds (i.e. ECs) were associ­
dumping, the distributing of pesticides, the use of non-biodegradable ated with an identified harmful health and environmental impact
materials, the use of fertilizers, harmful greenhouse gases, the disposal (Fig. 1). For example, pharmaceutical chemicals designed specifically to
of sludge, and the waste of other dangerous chemicals, that face serious elicit a biological response in a specific organism may also elicit the
environmental consequences (Khan et al., 2021a; Rasheed et al., 2019b; same response in non-specific creatures following persistent exposure to
Ziraba et al., 2016). A broad and increasing variety of human-made even minute amounts of those chemicals (Houtman, 2010; Wilkinson
substances that are regularly found in water but have only lately been et al., 2016).
discovered as major water contaminants are known as emerging con­ Additionally, some endocrine disruptors (EDs) have been discovered
taminants (ECs) (Gomes et al., 2018, 2020; Khan et al., 2019; Ouda as interfering with the endocrine function of the body and hence have
et al., 2021). There are a number of synthetic substances that are detrimental human and animal reproductive, neurological, develop­
essential for contemporary societies around the world, namely mental and immunological impacts (Gomes et al., 2018; Houtman,

* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (S. Khan), [email protected] (Mu. Naushad).

https://doi.org/10.1016/j.envres.2021.112609
Received 16 November 2021; Received in revised form 13 December 2021; Accepted 19 December 2021
Available online 28 December 2021
0013-9351/© 2021 Elsevier Inc. All rights reserved.
S. Khan et al. Environmental Research 207 (2022) 112609

2010). They are ubiquitous throughout the ecosystem but are most often effective remediation strategies. As a result, long-term purification of
detected in wastewaters. The largest examined chemicals include the EC-polluted water is an ongoing concern (Hwang et al., 2016; Khan
broad array of EDs displayed in Fig. 2. Corcoll et al. (2014) have shown et al., 2021c; Rodriguez-Narvaez et al., 2017).
that anti-inflammatory pharmaceuticals like as naproxen and diclofenac It is critical to note that prior to the detrimental effects of climate
can result in reduced health of biofilm stream organisms. Many addi­ change compelling communities to reuse water without sufficient pro­
tional emerging contaminants, such as musk scents or plasticizers, are tection, environmentally acceptable and evidence based initiatives
still unknown in terms of their hazard to humans and the environment, should be implemented to mitigate potential risks to humans and the
but have been identified in adipose tissue, breast milk and blood (Wil­ environment. Identifying and developing technological trends and gaps
kinson et al., 2015; Wombacher and Hornbuckle, 2009). In this context, in knowledge about the removal of emerging contaminants from water is
their monitoring throughout the environment has risen to a significant a top priority for researchers and ecologists in order to ensure that the
existential problem, and it is critical to improve the performance of general public has access to safe drinking water (Hwang et al., 2016;
wastewater management in order to combat environmental contami­ Khan et al., 2020; Rodriguez-Narvaez et al., 2017). In light of the fore­
nation. Curiously, the World Health Organization (WHO) gave consid­ going, the primary goal of this study is to compile a list of emerging
erable importance to the diagnosis and prevention of emerging hazards contaminants and to evaluate process treatment techniques for their
in wastewater, drinking water, surface water and groundwater, and they elimination in order to avoid potential health concerns to humans and
released an exclusive research detailing the presence of medicines in other organisms.
drinking water and groundwater, as well as the related health and
environmental risks (WHO, 2011). While substantial scientific research 2. Emerging contaminants
has been done on environmental contaminants including hydrocarbons
and hazardous compounds in wastewater, there have been few sys­ The phrase “emerging contaminant” refers to environmental hazards
tematic examinations into the occurrence of ECs and the recording of related with the emergence of new contaminants with uncertain effects

Fig. 1. Life-cycle distribution of emerging (micro)-pollutants from sources to receptors viewpoint. (Reprinted from Rasheed et al. (2019a), with permission of The
Authors. Published by Elsevier Ltd. copyright (2018).

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S. Khan et al. Environmental Research 207 (2022) 112609

Fig. 2. Chemical structures of EDs: (A) bisphenol-A, (B) triclosan, (C) nonylphenol, (D) 17β-estradiol, (E) genistein, (F) β-sitosterol, (G) dichlorodiphenyltri­
chloroethane (DDT), (H) endosulfan, and (I) estradiol (E2). (Reprinted from Bilal et al. (2018c), with permission of Elsevier B.V.copyright (2018).

but the potential for significant harm (Bao et al., 2015; Khan et al., 2014; Rathi et al., 2021a; Wilkinson et al., 2017). Fig. 3 depicts the
2018b; Naidu et al., 2016). Major progress in recognizing organic con­ origins of emerging pollutants. To date, a number of techniques have
taminants from industrial wastewater also includes developing new been developed to mitigate the negative consequences of the destruction
technologies for analyzing new and emerging pollutants throughout the and elimination of emerging pollutants. Several previous or continuing
past century (Dsikowitzky and Schwarzbauer, 2014; Naidu et al., 2016). research have focused on pollution removal and disposal utilizing a
The ubiquitous occurrence of emerging pollutants, as well as their variety of treatment methods, including chemical, biological and phys­
detrimental environmental and health repercussions, is becoming a ical techniques (Bilal et al., 2019a; Rathi et al., 2021a).
terrible issue (Juliano and Magrini, 2017b; Khan et al., 2021a; Stewart
et al., 2014). Emerging pollutants from the pharmaceutical and cosmetic
2.1. Sources of emerging contaminants
sectors, as well as chemicals that change the endocrine system, fire re­
tardants, and fertilizers, are all of great concern. Various forms of
Pharmaceutical industry, antibiotics, pesticide, surfactants, flame
emerging contaminants are dumped into natural environments, either
retardants, fertilizer industry, artificial sweeteners, hormones, per
intentionally or unintentionally, with or without regulated treatments,
fluorinated compounds, illegal drugs, clothing adhesives, solvents for
posing health risks and affecting the overall living situation (Naushad,
cleaning, antibacterial, ointments, foam for cushions, cosmetics, beauty

Fig. 3. Roots of Emerging Contaminants. (Reprinted from Rathi et al. (2021a), with permission of Elsevier B.V.copyright (2020).

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S. Khan et al. Environmental Research 207 (2022) 112609

care, sun protection, personal care products, and drinks and packaged conventional treatment plants that rely primarily on micro-organisms,
food are the main sources of emerging pollutants (Rathi et al., 2021a; because of their complex chemical composition and low ability,
Richardson and Kimura, 2017). Emerging micropollutants, such as cannot obviously kill those types of organic chemicals and that their
pharmaceuticals, endocrine disruptors, cosmetics, nanoparticles, and elimination rate is only around 10 percent. The most normally report
fluorinated chemical products, pose a significant threat to the health and pharmaceuticals in drinking water and wastewater include: fluoxetine,
well-being of humans and marine organisms due to their presence in the lipid-lowering drugs, antacids, ciprofloxacin, diclofenac, steroids, beta
environment (Besha et al., 2020; Sivaranjanee and Kumar, 2021; Tijani blockers, clofibric acid, analgesics, antipyretics, antibiotics,
et al., 2016). The primary sources of emerging pollutants are depicted in anti-inflammatory drugs, stimulants, salicylic acid, antidepressants,
Fig. 4. nitroglycerin, and propranolol (Naushad et al., 2019; Snyder, 2008).
First class, various substances including ibuprfen, enalapril, and acet­
2.1.1. Pharmaceutical sector aminophen were mostly eliminated during treatment. Second class re­
Pharmaceuticals are becoming increasingly troublesome contami­ agents such as lipid regulators have not been completely eliminated;
nants, yet they have been found in minute amounts in sources of water however their levels are much smaller than those in influential reactants
all across the world (Chinnaiyan et al., 2018; Patel et al., 2019). Phar­ following treatment. In contrast to influential effluent, sewage water of
maceuticals are a class of chemicals that are widely utilized in nutrition, effluents contained a group 3 of compounds, including ansiolitics,
diagnostics, treatment, and prevention (Patel et al., 2019; Rico et al., macrolide, and antibiotics, which were not detected in influential
2013; Tran et al., 2015). A critical emerging contaminant is the phar­ effluent. Last-class pharmaceuticals such as simvastatin, paroxetine and
maceutical industry. Other critical emerging contaminants include illicit sulfamethazine were never detected in significant amounts in waste­
medicines, hormones, antibiotics, and hormone-like substances. These water effluent (Gracia-Lor et al., 2012; Rathi et al., 2021a).
contaminants are important because of their widespread presence in In 2004, illicit drugs were discovered in aquatic environments for the
aquatic ecosystems, contamination of fresh water supplies, and potential first time. It has been discovered in wastewater, groundwater, and sur­
adverse effects on the environment and human health (Cizmas et al., face water in recent years. While doses in surface water are normally
2015; Patel et al., 2019; Sharma et al., 2019). Waste dilution following minimal, certain wastewaters may contain up to μg L− 1. Cocaine, 2-eth­
release of drugs into the water system efficiently mitigates environ­ ylidene-1, benzoylecgonine, methadone and their metabolites, 5-
mental concerns (Gros et al., 2010; Khan et al., 2019). A variety of drugs dimethyl-3, 3-diphenylpyrrolidine were more frequently detected,
are widely administered to livestock in order to reduce illness and though at lower ng L− 1 concentrations than other contaminants. Tri­
improve the condition of the animals. closan is a common antibiotic found in toothpastes and hand soaps, and
In light of the fact that around 3000 compounds are currently being it is also frequently found in the air. Hormones’ capacity to have an
utilized in pharmaceutical goods, only a tiny proportion of these sub­ androgenic and estrogenic effect on biodiversity increased their signif­
stances have been evaluated in the field. Scientists and regulators have icance as an environmental contaminant (Behera et al., 2011; Kitamura
evaluated even if presence of ng L− 1 dosages exposed to air might cause et al., 2005; Naushad and Alothman, 2015). 17β-estradiol, equilenin,
to harmful repercussions in wildlife or humans (Khan et al., 2018a; equiline, estriol, mestranol, estrone, 17α-estradiol, and norethindrone
Richardson and Kimura, 2017). Pharmaceuticals entered the atmo­ are examples of organic or inorganic hormones that can enter the at­
sphere most frequently through human waste, the dumping of unwanted mosphere through cultivation and processed wastewater, and which are
medications, and the usage of pharmaceuticals in agriculture. Ground­ still not completely eliminated (Yang et al., 2011). Photocatalysis, which
water and surface water samples were found to contain a wide range of uses the TiO2 semiconductor as a catalyst, has also proven to be an
medications that had been associated with wastewater discharge effective method of water purification. Additionally, the efficiency of
(Naushad et al., 2019; Stuart et al., 2012; Tran et al., 2014). In intensive this oxidative approach has been demonstrated for the breakdown of
animal farming, medicines can also have an indirect impact on the pharmaceutical compounds (Kanakaraju et al., 2014; Naushad and
environment through the use of manure and purines as organic fertil­ Alothman, 2015; Wang and Xu, 2012).
izers, and they can be transferred to living organisms through the food Table 1 contains a list of emerging pollutants in pharmaceuticals, as
supply chain. Pharmaceuticals used in fisheries are intentionally dis­ well as information on their characteristics. In pharmaceuticals, there
charged into surface water. Scientific research has shown that are several new pollutants that pose a concern to animals, marine

Fig. 4. Major Causes of Emerging Contaminants. (Reprinted from Rathi et al. (2021a), with permission of Elsevier B.V.copyright (2020).

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S. Khan et al. Environmental Research 207 (2022) 112609

Table 1
Pharmaceuticals, pesticides, and personal care product contaminants with characteristics.
Pharmaceuticals Type Emerging Molecular Octanol- Acid dissociation Influent Effluent References
contaminants weight coefficient Log coefficient, pKa concentration ng concentration ng
Kow L− 1 L− 1

Analgesics and anti- Naproxen 230.3 3.18 4.2 2584 111 Behera et al.
inflammato ries (2011)
Analgesics and anti- Codein 299.37 1.19 8.31 242 208 Tran et al. (2018)
inflammato ries
Analgesics a and anti- Ibuprofen 206.3 3.97 4.91 2265 40 Behera et al.
inflammato ries (2011)
Analgesics and anti- Diclofenac 296.1 0.7 4.2 131 24 Behera et al.
inflammato ries (2011)
Analgesics a and anti- Antipyrine 188.23 0.54 1.3 2260 690 Acero et al.
inflammato ries (2012)
Analgesics and anti- Ketoprofen 254.3 3.12 4.5 202 12 Behera et al.
inflammato ries (2011)
Analgesics and anti- Paracetamol 151.16 0.46–0.49 9.86 1746–43223 25–4319 Wadhah Hassan
inflammato ries (2017)
Analgesics and anti- Acetaminop hen 151.2 0.46 9.4 7460 10 Behera et al.
inflammato ries (2011)
Antibiotics Trimethopri m 290.3 0.91 6.8 205 63 Behera et al.
(2011)
Antibiotics Amoxicillin 365.4 0.87 2.7 6516 1670 Tran et al. (2018)
Antibiotics Azithromyc in 749.00 4.02 7.34 2020 60.1–980 Tran et al. (2018)
Antibiotics Lincomycin 406.54 0.29 7.9 8176 9089 Behera et al.
(2011)
Antibiotics Sulfametho xazole 253.3 0.89 5.7 120 57 Behera et al.
(2011)
Antibiotics Flumequine 261.25 1.31 6.1 60 10 Acero et al.
(2012)
Antibiotics Metronidaz ole 171.16 − 0.02 2.38 42 28 Verlicchi et al.
(2012)
Gemfibrozi l Anti- Cholesterol 250.34 4.77 4.7 222 17 Behera et al.
(2011)
Endocrine Disrupter Propylparab en 180.20 3.04 7.9 2180 19.7 Ma et al. (2018)
Endocrine disrupting Bisphenol- A 228.3 3.3 9.6 55.6–5850 123 Ghosh et al.
compound (2013)
Endocrine Disrupter Methylpara ben 152.15 1.96 8.4 334 11 Puerta et al.
(2020)
Anti- inflammato ry Ketorolac 255.27 2.15 4.0 800 504 Bueno et al.
(2012)
Hormone Estradiol 272.2 4.01 10.46 4 0 Behera et al.
(2011)
Hormone Estrone 270.4 3.13 10.34 47 6 Behera et al.
(2011)
Hormone Estriol 288.4 2.8 10.38 415 0 Behera et al.
(2011)
Psychiatric drugs Carbamazep ine 236.3 2.45 13.9 72 55 Behera et al.
(2011)
Psychiatric drugs Caffeine 194.19 − 0.07 10.4 2349 18 Behera et al.
(2011)
Psychiatric drugs Diazepam 284.7 3.08 3.4 76 1 Wang and Wang
(2016)
Psychiatric drugs Primidone 218.3 1.12 12.3 10.8 2.5 Walraven and
Laane (2008)
Psychiatric drugs Salbutamol 239.32 0.64 9.3 13 12 Verlicchi et al.
(2012)
β-blockers Atenolol 266.3 0.16 9.6 5113 2772 Behera et al.
(2011)
β-blockers Propranolol 259.3 3.48 9.45 9.56 8.3 Tran et al. (2018)
β-blockers Metoprolol 267.3 2.15 9.6 4 3 Behera et al.
(2011)
β-blockers Metoprolol 342.41 1.72 9.6 79,500 268 Dolar et al.
(2012)
β-blockers Sotalol 272.4 0.24 8.35 530 320 Verlicchi et al.
(2012)
Type of pesticides
Pesticides Isoproturon 206.29 2.22 – 55 100 Liu (2010)
Pesticid e Lindane 290.8 3.72 – 7.3 2.1 Kuntz and Warry
(1983)
Pesticid e Atrazine 215.69 2.43 2.27 34.7 755 Ward and Weber
(1968)
Pesticid e DDT 215.7 2.61 1.7 0.025 41.3 Faroon and Harris
(2002)
Pesticid e Metolachlor 283.8 3.13 − 1.34 530 15 Snyder et al.
(2007)
(continued on next page)

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S. Khan et al. Environmental Research 207 (2022) 112609

Table 1 (continued )
Pharmaceuticals Type Emerging Molecular Octanol- Acid dissociation Influent Effluent References
contaminants weight coefficient Log coefficient, pKa concentration ng concentration ng
Kow L− 1 L− 1

Bactericide Triclosan 289.6 4.76 7.8 10 734 Loraine and

Pettigrove (2006)
Biocide Hydroxybipheny l 170.21 3.27 9.8 700 100 O’Malley (2010)
Personal care products
Sunscreen agents Oxybenzone 228.2 3.79 – 2616.8 772 Wang and Wang
(2016)
Sunscreen agents Octocrylene 361.5 6.9 – – 153 Wang and Wang
(2016)
Fragrances Galaxolide 258.4 5.9 – 4839.3 4721 Snyder et al.
(2007)
Fragrances Musk xylene 297.3 4.4 – 83.3–120 25–36 Bueno et al.
(2012)
Fragrances Musk Ketone 294.3 4.3 – 466.6–1366.6 140–410 Snyder et al.
(2007)

animals and humans as well as to the environment, even at low bio-accumulate in living organisms, plants (Gani and Kazmi, 2017;
concentrations. Gavrilescu, 2005). When emerging pollutants are established in the
agricultural ecosystem, they will confront the similar fate and transit
2.1.2. Personal care products mechanisms that are experienced by many existing pollution categories.
Personal care products are a collection of common chemical products Emerging pollutants can be polluted biologically, physically, or chemi­
used for a variety of purposes, such as nutrition, beauty, and cleaning. cally; they can adhere to soil detritus, be taken up by roots, dissolve in
Personal care products such as cosmetics, skin care, hair care, cleaning groundwater, or be transferred to surface water via precipitation and
products, and scents were included. Skincare and personal care products irrigation water. The extent to which each of these processes can take
are widely used around the world; as a result of their everyday use, they place is determined by the fundamental physical properties of emerging
are constantly released into the atmosphere in significant quantities pollutants, such as solubility; the substance’s affinity to organic matter
(Caliman and Gavrilescu, 2009; Khan et al., 2018b; Kim et al., 2016). and other materials in the soil; and the substance’s reaction, as well as
Individual actions are increasing the number of emerging contaminants the soil and environmental conditions (Boxall, 2012; Gavrilescu, 2005;
discharged into the environment daily, which reflects the exponential Khan et al., 2013). Endosulfan, hexachlorocyclohexane and dichlor­
growth in the use of a extensive array of commodities, such as prettiness odiphenyltrichloroethane (DDT) were among the most common pesti­
and personal care (Caliman and Gavrilescu, 2009; Kasprzyk-Hordern cides used. diazinon, methyl parathione, chlorpyriphos, bentazone,
et al., 2009). The majorities of these substances is bioactive and are dimethoate, phorate, phosphamidone,cyanazine, alachlor, terbuthyla­
classified according to their ability to retain and bioaccumulate, posing a zine, simazine, and atrazine are other products (Gani and Kazmi, 2017;
threat to human health and the environment (Juliano and Magrini, Köck et al., 2013). Table 1 contains a list of emerging pesticide con­
2017a). Emerging contaminants are frequently used in skin care prod­ taminants and their characteristics. These are the various emerging
ucts and can potentially reach dangerous levels for public (Reid et al., toxins as a result of pesticide use. Hexachlorocyclohexane and dichlor­
2019; Sharma et al., 2019; Wang and Wang, 2016). The highest quan­ odiphenyltrichloroethane accounted for roughly 67 percent of all
tities of emerging contaminants were identified in cosmetics, with ZnO pesticide pollutants.
and TiO2 nanoparticles emerging as major possible contaminants. The
following are the most likely emerging pollutants in personal care 2.1.4. ECs based on PACs
products: TiO2 nanoparticles, microplastics, polydimethylsiloxane, UV Polycyclic aromatic contaminants (PACs) constitute organic pollut­
filters, butylated hydroxylanisole, insect repellents, disinfectants con­ ants that consist of more than one aromatic ring linked to a unique
taminants like triclosan and hydroxytoluene, fragrances contaminants structure. However, a great diversity of polycyclic aromatic contami­
like tonalide, phantolide, and galaxolidecelestolide, preservatives nants have been studied for decades and only a tiny percentage of
diethyl phthalate, ZnO nanoparticles, octinoxate benzophenone, polycyclic aromatic contaminants (around 16) are classified as toxins in
methoxycinnamate, parabens, and butylparaben (Dhanirama et al., the “US Environmental Protection Agency” (Banger et al., 2010).
2012; Miege et al., 2009; Montes-Grajales et al., 2017). Polycyclic musks Aromatic impurities present in the fused ring are semi-volatile, hy­
are used as affordable fragrances in shampoos, washing powder, hair drophobic, and environmentally persistent. The hydrophobicity and
products, laundry detergents, and cosmetics techniques (Abedi et al., volatility largely depend on the fusion of some aromatic ring. The hy­
2018). Its application mostly on the exterior of the skin surface increases drophobic character of the material rose as the frequency of rings
the chance of its occurrence in greater quantities throughout the envi­ increased, but the volatility of the pollutant declined. The combustion
ronment without causing metabolic alterations (Gani and Kazmi, 2017; reaction and decomposition of coal, hydrocarbons, and other biofuels
Sharma et al., 2019). Table 1 contains a list of emerging pollutants and are the most significant sources of these pollutants (Abdel-Shafy and
their features identified in personal care products. Because cosmetics are Mansour, 2016; Berthiaume et al., 2021). Due to their excellent volatile
something that we use on a routine basis, even a trace amount of these qualities, these aromatic pollutants quickly combine with soil, water,
contaminants can be harmful to humans, animals, and the ecosystem. air, and food (Berthiaume et al., 2021; Srogi, 2007; Xu et al., 2016).
Human beings are largely influenced by breathing, smoking, and skin
2.1.3. Pesticides contact (Navarro et al., 2017).
Pesticides consist of a varied spectrum of agents with physiochemical Studies show that over 50% of PACs are carcinogenic, others lead to
qualities to limit or prevent the spread of hazardous insects, weeds and oxidative stress, diabetes, fetal disorder, infertility, cardiovascular and
microbes such as microorganisms. Generalized pesticides are divided inflammatory diseases (Berthiaume et al., 2021; Ferguson et al., 2017;
into four types: herbicides, fungicides, insecticides, and bactericides. It Yang et al., 2017). Indeno [1,2,3-cd] pyrene, benz [a]anthracene, benzo
enters maritime environments by runoff from the application site, and [a] pyrene (BaP), dibenz [a,h] anthracene, chrysene, benzo [k]fluo­
depending on the solubility of the chemical, these contaminants may ranthene and benzo [b]fluoranthene are the most deadly carcinogenic

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S. Khan et al. Environmental Research 207 (2022) 112609

chemicals. (Banger et al., 2010). Furthermore, these polycyclic aromatic and Pandey, 2005; Naushad and Alothman, 2015). There have been
contaminants are associated with a number of short-term adverse effects several methods invented and used to remove dye-based contaminants
such as nausea, irritation of the eye, gene mutations, itchy skin and from wastewater produced by the industry, including chemical treat­
protein damage. Because of the high toxicity of PACs, as well as the fact ment, ionpair extraction, biosorption, coagulation and flocculation
that they exist as a group, a greater understanding of their composition (Çınar et al., 2008; Misra and Pandey, 2005; Rathi et al., 2021b).
can aid in the management of their effects and severity. Extensive use However, in practice, these treatments have been shown to be
and handling of polycyclic aromatic hydrocarbons should be avoided to expensive, time-consuming, and as a result, the overall treatment pro­
reduce their metabolism impacts on people (Ramesh et al., 2004; Santos cedure may result in additional contamination concerns (Bilal et al.,
et al., 2019). 2018a). For this reason, the availability of increasingly efficient tech­
nologies is critical in the combat against these environmental toxins that
2.1.5. ECs based on dioxins and PCBs are of great public concern. Technical and economic feasibility of ap­
A wide range of environmental pollutants, including polychloro- proaches are determined by a variety of processing criteria such as the
dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and type of dyestuffs, waste effluent content, the operating costs, and the fate
polychloro-dibenzo-p-dioxins (PCDDs) can be found in anthropogenic of waste products generated in the environment. Biological treatments
environments. Because of their poor water solubility, low vapor pres­ offer better possibilities compared to chemical treatment systems that
sure, and high octanol-water coefficient, these pollutants are most can effectively eliminate dyes from enormous quantities of industrial
commonly found in the form of suspended solids in the environment effluents at a cost whilst retaining high efficiency levels (Chatha et al.,
(Reddy et al., 2019; Sany et al., 2015). The original sources of these 2017). There is no doubt that integration of green catalysts such as en­
elements are metal smelting, burning of pharmaceutical and toxic ma­ zymes, which are ecologically sound compared to chemical processes,
terials, fossil fuel combustion activities, and open burning of automo­ can substantially reduce the overall cost-effectiveness of the process
biles. The primary pollutants produced by combustion are the precursors (Chatha et al., 2017; Naushad and Alothman, 2015). Table 2 summarizes
that remain after incomplete combustion, as well as their derivatives a collection of comparative evaluations of peroxide-assisted removal of
(McKay, 2002; Reddy et al., 2019; Stanmore, 2004). They are extremely industrial dye-based contaminants.
dangerous and harmful and induce a variety of serious disorders,
including carcinogenesis, cardiovascular illness, behavioral changes, 2.1.7. Additional sources of ECs
immune system disruption, tumor promotion, disruption of the neuro­ A surfactant is a manufactured material that is widely utilized in the
logical, teratogenicity and endocrine systems (Sany et al., 2015; Srogi, creation of paints, emulsion, pesticides, cleaning agents, cosmetic and
2008). They are very stable in nature and readily bioaccumulative. other industrial products (Mandaric et al., 2015; Mattei et al., 2014).
These contaminants have a half-life of weeks to months, depending on Apart from the fact that surfactants caused foam to build in bodies of
their surroundings, and rises as body fat levels increase (Emond et al., surface water, they were also harmful to aquatic life. The toxicity of
2005; Srogi, 2008). The impact of dioxin-like (DL) chemicals on the surfactants is mostly governed by their capacity to support and penetrate
environment is largely determined by the interaction of aryl hydrocar­ marine cellular membranes. They were included not just as household
bons with their receptors. There are different types of PCBs, for example, and commercial cleaners, but also as emulsifiers, paints, antifoamers,
those that are unable to bind to the receptor are referred to as non-DL and the pesticide triclosan (González et al., 2012; Mattei et al., 2014;
PCBs and are associated with neurotoxicity, immunological suppres­ Papaevangelou et al., 2016). Surfactants such as lignin sulfonates,
sion, and endocrine disruption (Hamers et al., 2011; Srogi, 2008). PCBs, alkylphenol ethoxylates linear alkybenzenesulfonates, and fatty alcohol
PCDDs, and PCDFs have a high lipophilicity, which allows them to infect ethoxylates are frequently utilized. Additionally, the lower molecules
food chains (Malisch and Kotz, 2014; Srogi, 2008). These negative such as octylphenol and nonylphenol, which are used to synthesize the
consequences are difficult to regulate since the cost and limited number alkylphenol ethoxylates surfactants, are relatively stable in the natural
of tests available to confirm the presence of DL-like compounds in ani­ environment (Gani and Kazmi, 2017; Priac et al., 2017).
mal feed. The most straightforward protection is to eliminate fatty foods, Certain kinds of chemicals were also of interest due to their char­
which are the most effective direction for these toxins to penetrate the acteristics. Bisphenol A and phthalates, both of which are employed as
body. The most successful method is to develop a biomarker that vali­ plasticizers, were investigated due to their potential for endocrine
dates the DL chemical’s binding to the target cell’s aryl receptor and disruption. Polycyclic aromatic hydrocarbons are a significant source of
determines their toxic levels, for example, gene microarray study of contamination as a result of fossil fuel combustion and forest fires
mononuclear cells (Kim et al., 2004). (ChooChuay et al., 2020; Faboya et al., 2020).
Caffeine, nicotine, and the nicotine metabolite cotinine are regularly
2.1.6. Toxic pollutants containing dyes identified in groundwater contaminated by sewage effluent. In
Poisonous compounds such as industrial applications created syn­ groundwater and marine ecosystems, elevated levels of sugar substitutes
thetic dyes and dye-containing harmful wastewater effluents are causing such as saccharin, sucralose, acesulfame, and cyclamate have been
environmental legislation and regulatory bodies to become increasingly detected as a result of the use, longevity, and durability of sewage runoff
worried about the destructive nature of these compounds. Adhering to pools (Stuart et al., 2012). Triethyl citrate is frequently used to preserve
severe environmental law and policies can provide the optimal approach foams, while butylated hydroxyanisole and butylated hydroxytoluene
for pollution prevention (Chatha et al., 2017; Naushad and Alothman, have also been used to prevent fat food poisoning. Other food in­
2015). Chemical substitution is another viable strategy for resolving this gredients include citronellal, camphor, heliotropin, eucalyptol, phenyl­
dilemma. It is defined as “the substitution or reduction of hazardous ethyl alcohol, citral, menthol, cis-3-hexenol, hexanoic acid, triacetin,
substances in products and processes by technological or organizational and terpineol. There’s a chance that several of these are oxidizing agents
methods in order to achieve similar functionality” (Oosterhuis, 2006). or endocrine disruptors (Stuart et al., 2012). The sources of emerging
Despite this widespread concern, the manufacturing industry consumes toxins listed above are drawn from a multitude of sectors.
a substantial amount of structurally diversified synthetic dyes such as
acidic, diazo, basic, azo, dispersion, reactive, anthraquinone, and 3. Consequences of ECs and current challenges
metal-complex, which are significant contributors of environmental
contamination (Bilal et al., 2018b; Misra and Pandey, 2005). The Naturally occurring or synthesized emerging contaminants have
discharge of these dyes and/or their degradation byproducts, which are been linked to proven or anticipated adverse effects on health and
frequently poisonous into major bodies of water poses a substantial environment. However, elucidating and recognizing the environmental
hazard to human health and the environment (Khan et al., 2020; Misra and health problems posed by toxic compounds is challenging due to a

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Table 2
Enzyme-mediated removal or degradation of dyes from industrial waste effluents.
Dyes containing effluents Enzyme used Immobilization support Removal or References
degradation (%)

Reactive blue 4 Ginger peroxidase Polypyrrole-cellulose-graphene oxide nanocomposite 99.0 Ali et al. (2018)
Dyes containing textile Manganese peroxidase Agarose beads 98.4 Bilal et al. (2017a)
industry effluents
Indigo Horseradish peroxidase Cross-linked enzyme aggregates 84.35 Bilal et al. (2017c)
Methyl orange Horseradish peroxidase Polyvinyl alcohol-alginate (PVA-alginate) beads 100 (Bilal et al., 2017e)
Methyl orange Horseradish peroxidase Cross-linked polyacrylamide gel >90.0 Bilal et al. (2018a)
Dyes containing textile Manganese peroxidase Cross-linked enzyme aggregates 84.2–100 Bilal et al. (2017b)
industry effluents
Methyl orange Horseradish peroxidase Cross-linked enzyme aggregates 94.26 Bilal et al. (2017c)
Basic red 9 Horseradish peroxidase Cross-linked enzyme aggregates 91.73 Bilal et al. (2017c)
Reactive black 5 Horseradish peroxidase Chitosan beads 97.82 Bilal et al. (2017d)
Rhodamin B Horseradish peroxidase Cross-linked enzyme aggregates 81.47 Bilal et al. (2017c)
Rhodamine 6G Horseradish peroxidase Cross-linked enzyme aggregates 73.60 Bilal et al. (2017c)
Remazol brilliant blue R Horseradish peroxidase Chitosan beads 82.17 Bilal et al. (2017d)
Reactive blue 4 Horseradish peroxidase Calcium-alginate support 87.23 Bilal et al. (2016c)
Congo red Horseradish peroxidase Chitosan beads 94.35 Bilal et al. (2017d)
Crystal violet Horseradish peroxidase Chitosan beads 87.43 Bilal et al. (2017d)
Reactive red 120 Horseradish peroxidase Calcium-alginate support 72.39 Bilal et al. (2016c)
Solar brilliant red 80 Ligninolytic enzymes – 100 Asgher et al. (2013b)
Reactive orange Horseradish peroxidase Calcium-alginate support 79.57 Bilal et al. (2016c)
Dyes containing textile Manganese peroxidase Chitosan beads 97.31 Bilal et al. (2016a)
industry effluents
Dyes containing textile Manganese peroxidase Calcium alginate beads 87.40 Bilal et al. (2016d)
industry effluents
Local textile dyes Manganese peroxidase Agar-agar gel 78.6–84.7 Bilal et al. (2016b)
Methyl orange Soybean peroxidase – 81.40 Chiong et al. (2016)
Methyl orange Luffa acutangula (luffa) – 75.30 Chiong et al. (2016)
peroxidase
Dyes containing textile Manganese peroxidase Sol–gel matrix 100 Asgher and Iqbal
industry effluents (2013)
Dyes containing textile Manganese peroxidase Sol–gel matrix 100 Asgher et al. (2013a)
industry effluents
Congo red dye Laccase (Poly (styrene-co-divinylbenzene)-graft-poly (cycliccarbonate 93.0 Bayramoglu et al.
methacrylate)] microsphere (2018)

paucity of data on their effects. Nonetheless, a grasp of their trans­ tested can simply be evaluated. A large number of antiinflammatory
portation process, tracking, and fate gives a clear picture of their impact pharmaceuticals are highly poisonous and hazardous to marine life
on the ecosystem and aquatic life. The aggravation of environmental and (naproxen, acetaminophene, and ibuproven), sulfamethoxazole, and
health hazards caused by these pollutants is mostly owing to the absence carbamazepine. The presence of these antibiotics in water has a sub­
of legislation regulating maximum levels limits for these emerging stantial effect on the performance of microbial activity and on the effi­
contaminants in wastewater. In the United Kingdom, a technique for ciency of wastewater treatment (Gonzalez-Martinez et al., 2014). It is
dealing with ECs and reducing their consequences was recently devel­ also possible to develop anti-resistance bacteria and anti-resistance
oped (European Commission, 2011). These ECs can readily be intro­ genes in host species because of their higher concentration. Similarly,
duced into food chains through the wastewater used for farming and EDCs damage the endocrine system by imitating, inhibiting, and altering
become directly effective for humans and animals (Bilal et al., 2019b; hormones. They are simply accumulated by animals through their diet,
Khan et al., 2021b; Vithanage et al., 2014). Notwithstanding its low causing significant disruptions in food chains. ECs produce abnormal
concentration ranging from ng L− 1 to μg L− 1, substantial long-term estrogen ratios, reproductive tissue dysfunction, and abnormal testos­
health concerns might arise (Bilal et al., 2019b; Boxall et al., 2012). terone ratios in fish (Gomes and Lester, 2003).
Multiple ECs and their derivatives have a negative effect on environ­ The majority of the EC’s effort has focused on surface water due to its
mental life because of their partial or incomplete biodegradability (Bilal enormous concentration, diversity, and potential for environmental
et al., 2019b; Kostich et al., 2014; Sarmah and Halling-Sørensen, 2007). degradation. In conclusion, ECs significant environmental challenges
include bacterial toxicity, earthworms, crops, wild animals, in­
3.1. ECs detrimental environmental impact vertebrates, frogs and fish and suppressing algae, bacteria and fungal
growth (Boczkowski and Hoet, 2010; Khetan and Collins, 2007; Maur­
In order to examine the environmental toxicity of ECs, a specialized er-Jones et al., 2013).
indicator needs to quantify the level of eco-toxicity of emerging con­
taminants in the aqueous and atmospheric environments. In this 3.2. ECs health concerns
perspective “crustacean Daphnia magna” is the most popular and
extensively examined method for analyzing environmental toxicity Numerous substances found in the environment are classified as
depending on their mobility (OECD, 2004). In this bioassay, ECs with a pollutants because of their negative impact on the environmental and
concentration between 10 and 100 mg L− 1 are classified as dangerous public health. There are a variety of everyday substances that are
substances, those with a concentration between 1 and 10 mg/L as toxic, considered pollutants, including medications, water disinfection by-
and those with a concentration less than 1 mg L− 1 are classified as products, perfluorinated compounds, and nanoparticles among others,
extremely toxic to water bodies (Cleuvers, 2003; europea, 1996). This as detailed in the preceding section. They are frequently available in
investigation also has certain disadvantages because of the spectrum of damaging environments due to their broad use in transportation, civi­
species that are employed for testing and various toxicological end­ lization, industry and farming (Ahmed et al., 2021; Castiglioni et al.,
points. In spite of these restrictions, the toxicity indication of the ECs 2015). In addition to their beneficial impacts on human health,

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S. Khan et al. Environmental Research 207 (2022) 112609

structure-based medications have certain adverse effects on target spe­ Although capillary electrophoresis is less sensitive than liquid chroma­
cies such as cells and organs (Castiglioni et al., 2015; Ullah et al., 2018). tography, immunoanalytical methods are more dependent on the anti­
According to this perspective, propranolol and fluoxetine exhibit body employed and have difficulties when attempting to determine
considerable acute toxicity to benthos and zooplankton (Brooks et al., multiple analytes at the same time, and microbiological assays are
2003; Jacob et al., 2016). The presence of several pharmaceutical largely dependent on the nature of the sample (Buchberger, 2011).
emerging contaminants in tiny quantities is not environmentally Modern sophisticated analytical techniques have made tremendous
damaging or public health; nevertheless, long-term exposure to these advancements recently, but there is still a need for more susceptible
small quantity emerging contaminants results in chronic toxic conse­ recognition and evaluation of unidentified chemicals, which is being
quences in humans and animals (Fawell and Ong, 2012; Fent et al., addressed by research and development. It is vital to establish
2006). Likewise, animal stomachs have the ability to absorb a consid­ cutting-edge identification strategies for unidentified ECs as analytes,
erable amount of veterinary antibiotics; nevertheless, 30–90 percent of which could argue for low-cost, accurate, and redundant methods that
these antibiotics are expelled through feces, are mixed with fresh water deliver faster and more accurate results than expensive, arduous, and
sources, and are regarded as environmental pollutants (Alcock et al., time-consuming approaches. Pretreatment of samples is critical for a
1999; Fawell and Ong, 2012). Antibiotic overuse in livestock has correct determination of ECs in samples. Previous research has mostly
resulted in the rapid expansion and development of new relied on liquid-liquid extraction. Solid phase extraction, on the other
antibiotic-resistant bacteria in the last few years. Perfluorinated com­ hand, has grown in popularity in recent years due to several advantages
pounds (PFCs), such as perfluorooctanesulfonate (PFO), are another over liquid-liquid phase extraction, including accuracy, practicality, and
type of EC that is extremely dangerous. They can induce cancer and accessibility. Pre-concentration of water samples is also recommended
damage liver adenomas (Corsini et al., 2014; Klaunig et al., 2012). Other before determining the final lower detection limits (LOD) and low
adverse effects of PFCs on human health include infertility, decreased quantification limits (LOQ), as it helps to reduce the LOD and LOQ
sperm production, and thyroid tissue difficulties (Corsini et al., 2014; levels. Several instrumental analyses of emerging pollutants are
Shrestha et al., 2015; Webster et al., 2014). The disturbance of devel­ included in Table 3. Numerous pre-concentration procedures have been
opmental activities, the hypothalamus pituitary thyroid axis, and described, including magnetic on-line solid phase extraction, solid phase
reproductive systems in humans and animals is the most serious health extraction, automated solid phase extraction, and the use of molecularly
concern associated with PPCPs (Corsini et al., 2014; Krause et al., 2012). grafted polymers (Moliner-Martínez et al., 2011). These techniques have
A common gasoline additive, methyl tertbutyl ether (MTBE), has the enhanced sample processing while reducing cross-contamination, effort,
potential to be a hazardous emergent environmental pollutant. It pro­ and expense (Thomaidis et al., 2012). During the sample pretreatment
motes kidney cancer and uterine, raises blood urea nitrogen levels. step of the process, the main concerns are reducing labor, lowering
MTBE also has a detrimental effect on the lungs of humans, causing LODs, and boosting selectivity. It is possible that nanomaterials will be
cancer (de Peyster et al., 2003). Due to their significant environmental one of the most fascinating choices for further investigation in this field.
and health implications, nanomaterials have recently been acknowl­ Current study has focused on nanomaterials with magnetic properties,
edged as a new class of ECs. Some nanomaterial ECs, according to the such as iron nanoparticles, as a possible substrate for solid phase ap­
researchers, is carcinogenic and have severe reproductive problems plications (Moliner-Martínez et al., 2011). These types of nanoparticles,
hazard. Lung cancer and reproductive instability are two more health as well as the further creation of innovative materials with enhanced
hazards linked to nanoparticles emerging pollutants (Enyoh et al., 2020; capability, could be another area of research.
Fryzek et al., 2003). Although considerable study has been directed
toward elucidating the process by which ECs interact with their envi­ 5. ECs treatment technologies
ronment over the last few years, it is still inadequate for some ECs.
Technologies relating to non-conventional water treatment have
4. Detection and quantification of ECs progressed over the time as innovative methods have been developed.
The major treatment technologies can be divided into three categories:
Most of the ECs may be decomposed into water due to its chemical phase-changing methods, and advanced oxidation methods, biological
properties, and through water cycles are potential threats to aquatic life, treatment methods. In this study, the emphasis is on sorption that is
the environment and humans (Nikolaou, 2013; Rasheed et al., 2019a). based on phase-changing methods as opposed to other methods. Because
Most recently, the number of environmental contaminants (ECs) that biological remediation and advanced oxidation approaches have
contain parent and derivatives in drinking water, groundwater, waste­ already been extensively described previously. The distinctive ECs
water and surface waters has been steadily increasing (Agüera et al., elimination capacity of various materials with sorption possibilities is
2013). It’s become an important scientific endeavor to recognize and addressed in the following sections using particular examples. It is
assess these ECs in various waters, which requires very susceptible assumed that these procedures have the same extraction efficiency as
systematic techniques for recognition at ng L− 1 scales. In order to those published, both before and after EC removal. A wide range of
effectively monitor and determine a wide range of ECs, it is vital to effective technologies has been developed to achieve phase-change of
create fast, responsive analytical procedures (Agüera et al., 2013). emerging contaminants from liquid phase to other phases, such as solid
Distinct analytical approaches for detecting and determining multi­ or gas. Sorption methods have been extensively explored for this pur­
ple forms of emerging contaminants in water have been developed and pose, and have been found to be effective in removing a wide range of
employed recently. Major approaches include liquid or gas chromatog­ contaminants (Khan et al., 2013, 2018a, 2018b, 2019, 2020, 2021b,
raphy and mass spectroscopy. Mass spectroscopy methods have 2021c; Khan and Şengül, 2016). The next sections provide a thorough
demonstrated remarkable outcome in the precision assessment of EC examination of a variety of phase-changing approaches for the sorption
samples of wastewater, principally due to sensitivity, specificity in of emerging pollutants from water.
recent times (Agüera et al., 2013). In order to find out ECs estimation at
the ng L− 1 level, advanced mass spectroscopic methods such as ion trap 5.1. Sorption of ECs onto activated carbon
and triple quadrupole are used; on the other hand, more advanced
methods such as linear ion traps quadrupole, quadrupole-time of flight, The surface area and high porosity of activated carbon have been
triple quadrupole, and quadrupole-linear ion trap are employed for the broadly used for successful elimination of certain pollutants (Al-Othman
morphological analysis of changed product (Nikolaou, 2013). The uses et al., 2012; Khan et al., 2018b, 2019, 2021b). The usage of activated
of immunoanalytical methods and capillary electrophoresis have all carbon has been shown to remove a wide range of compounds with a
been reported as additional analytical approaches for EC measurement. high capability of >90% and to be able to selectively remove some ECs

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Table 3
Instruments to detect emerging pollutants.
Emerging Contaminants Instruments set up Concentration Operation condition References
range
1
ECs of all kinds can be Gas Chromatography – Gas <1 mg L− Solvent vent time 6 s, inlet solvent vent pressure Lebedev et al. (2020)
examined. Chromatography setup − 5 psi, inlet solvent vent flow − 100 ml/min, inlet
purge time— 120 s, and inlet purge flow— 20 ml/
min
1
Levamisole Ultra high pressure liquid chromatography- 9.2 ng L− – Snow et al. (2015)
tandem mass spectrometry
1
Anthelmintic compounds High performance liquid chromatography 43.27 ng L− – Snow et al. (2015)
coupled to quadrupole linear ion trap mass
spectrometry
1
Carbamazepine Supercritical–fluid chromatography 0.10–1.59 μg L− SD < 9.2% (del Carmen
coupled with diode- array detection Salvatierra-Stamp et al.,
2015)
1
Bisphenol A Supercritical –fluid chromatography 0.10–1.59 μg L− SD < 9.2% (del Carmen
coupled with diode- array detection Salvatierra-Stamp et al.,
2015)
1
17α-ethinyl estradiol Supercritical –fluid chromatography 0.10–1.59 μg L− SD < 9.2% (del Carmen
coupled with diode- array detection Salvatierra-Stamp et al.,
2015)
1
17β-estradiol Supercritical –fluid chromatography 0.10–1.59 μg L− SD < 9.2% (del Carmen
coupled with diode- array detection Salvatierra-Stamp et al.,
2015)
1
Triclosan Supercritical –fluid chromatography 0.10–1.59 μg L− SD < 9.2% (del Carmen
coupled with diode- array detection Salvatierra-Stamp et al.,
2015)
1
Glyburide Supercritical –fluid chromatography 0.10–1.59 μg L− SD < 9.2% (del Carmen
coupled with diode- array detection Salvatierra-Stamp et al.,
2015)
1
Pharmaceutical Ultra high pressure liquid chromatography- 1.9 ng L− – Snow et al. (2015)
compounds and personal tandem mass spectrometry
care products
1
Thiabendazole Ultra high pressure liquid chromatography- 0.2 ng L− – Snow et al. (2015)
tandem mass spectrometry
4-hydroxyphenyl a cetic Gas Chromatography – Mass Spectroscopy 0.92 ng L− 1– 600 SD – 4.83% Wu et al. (2010a)
acid ng L− 1
Antibiotics High pressure liquid chromatography - Mass 0.1 ng L− 1to 3.6 – Snow et al. (2015)
Spectroscopy/Mass Spectroscopy in positive ng L− 1
electrospray mode
Dehydrocholic acid Gas Chromatography – Mass Spectroscopy 0.92 ng L− 1– 600 SD – 4.83% Wu et al. (2010a)
ng L− 1

SD= Relative standard deviations.

from water (Baccar et al., 2012; Bernal-Romero del Hombre Bueno et al., carbon were used, the rate of diclofenac removal was greater than 90%,
2019). An example of their selectivity is the elimination of ciprofloxacin however when Filtrasorb 400 was used, the rate of diclofenac removal
with activated carbon. By using activated carbon, “ciprofloxacin” may was lowered (Baccar et al., 2012). It has been shown that activated
be eliminated almost immediately, bringing the total concentration carbon derived from a number of sources, such as sugar beet pulp,
down to levels below the detection limit (Renew and Huang, 2004; peanut hulls, coconut, shell and wood that has been activated with
Wang et al., 2015). It has been shown that using activated carbon for a phosphoric acid may eliminate tetracycline from wastewater. Sugar beet
range of contaminants can reduce pollutants by 90 percent, but only pulp and peanut hulls were eliminated in excess of 90%, whereas wood
when used for long periods of time (Huang et al., 2014; Jośko et al., was removed in excess of 75% and coconut shell was removed in excess
2013; Stalter et al., 2010). Yang et al. (2011) demonstrated the detection of 30% (Torres-Pérez et al., 2012). The reason for the minor value of
and elimination of 19 pharmaceutically active chemicals and personal coconut shell elimination is related to the carbon composition of the raw
care items in a high-performance wastewater treatment system. During resources, which is composed of compact fibers that result in lower pore
the one year study period, specimens were gathered monthly from diameters, and the lack of additional activation inhibits the formation of
January to December 2008 and 24-h composite specimens were taken new pores and/or increases the size of accessible pores (Al-Othman
following multiple treatments in the wastewater reclamation facility, et al., 2012; Bhatnagar et al., 2013; Yunus et al., 2020). In general,
including primary clarification, membrane filtration, activated carbon greater outcome in the elimination of emerging contaminants have been
sorption, sludge biological remediation, ozonation and granular media obtained when activated carbon from water has been used. For tetra­
filtration. Fig. 5 shows the elimination of a chosen group of emerging cycline, the elimination rate ranges from 30% to >99% when using
contaminants such as primidone, levofloxacin, erythromycin, ibuprofen, coconut shell activated carbon, whereas the rate for ciprofloxacin, when
diclofenac, trimethoprim, caffeine, ciprofloxacin, carbamazepine, N, utilizing the “Norit Rox activated carbon” is >99% (Ahmed et al., 2015;
N-diethyl-m-toluamide (DEET), and lincomycin through the use of Robles-Molina et al., 2014). Calgon Filtrasorb 400 has been shown to
activated sludge treatment and microfiltration (Yang et al., 2011). remove diclofenac in small quantities, with elimination rates as low as 5
The source of activated carbon is crucial in determining the variation percent (Homem and Santos, 2011), but norfloxacin and caffeine were
in extraction yield, as diverse sources eliminate at various rate. For completely eliminated. However, activated carbon derived from waste
example, acetaminophen is sorbed at a rate of greater than 90% when products shown promising outcomes while considerably reducing the
activated carbon produced from wood is used, but it is adsorbed at a rate presence of target ECs such as paracetamol, antibiotics and
of 60–87% when activated carbon derived from other sources (Cabrita anti-inflammatory drugs (Baccar et al., 2012; Bueno et al., 2012; Mir­
et al., 2010). Likewise, when olive waste cake and granular activated asole et al., 2016). Sorption can also be used in association with other

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S. Khan et al. Environmental Research 207 (2022) 112609

Fig. 5. Removal efficiency of targeted PPCPs by activated sludge biological treatment and membrane filtration. (The number above the X-axis refers to the number of
samples that were analyzed and met the quality assurance criteria) Reprinted from Yang et al. (2011), with permission of Elsevier Ltd. copyright (2011).

treatment approaches to efficiently remove emerging contaminants. For the viability of large-scale procedures, which makes them less effective
instance, Acero et al. (2012) explored removing ECs from water using a in terms of practical application.
combination of activated carbon remediation, coagulation, and ultra­
filtration. The combined treatment approaches removed specific pol­ 5.2. Sorption of ECs onto biochar
lutants at a rate of between 84 and 88 percent, based on the chemical
oxygen demand. Nonetheless, little is known about the influence of It is known as biochar, and it is a charcoal-based product that is often
other factors on sorption-based technologies and their effectiveness. It is used to improve soil quality. Biochar is produced from biomass by a
also difficult to scale-up research studies and variables for establishing process called pyrolysis, which is a high-temperature, no-oxygen

Fig. 6. Sorption mechanisms of emerging contaminants on modified biochar. Reprinted from Cheng et al. (2021), with permission of Elsevier Ltd. copyright (2021).

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S. Khan et al. Environmental Research 207 (2022) 112609

heating process analogous to that used to make carbonaceous materials footprints into account is crucial for sustainable uses.
(Luque et al., 2012; Xie et al., 2014). In recent years, the sorption of ECs
on biochar has been extensively investigated (Cheng et al., 2021; Luque 5.3. Sorption of ECs onto nanomaterials
et al., 2012; Teixidó et al., 2011). During the sorption processes,
modified biochar yields both physical and chemical sorption, however Carbon nanotubes (CNTs) are a type of carbon allotrope that exhibits
the dominating sorption mechanisms may vary when adsorbing a variety of sorption qualities depending on their physical and chemical
different contaminants. A significant electron donor-acceptor (EDA) characteristics, size, interior angles, the growth of the initial sheet, de­
contact exists in general between the aromatic ring of the π donor on the gree of curl, and the technique of formation (Kim et al., 2014a, 2014b;
modified biochar surface and the π -protonated adsorbate. In addition, Rakhi, 2019). They have a graphite-like structure. CNTs are often
electrostatic interactions, hydrogen bonding, surface complexation, classed as single-walled nanotubes (SWNTs) with an internal diameter of
cation exchange, and non-specific van der Waals interactions may all around 1 nm and multi-walled nanotubes (MWNTs), which are
occur during the sorption process (Peiris et al., 2017) (Fig. 6). The ef­ composed of several tubes or laminated graphene layers (Kim et al.,
ficacy of biochar in treating and adsorbing ECs is reliant on the pyrolysis 2014a; Ren et al., 2011). Fig. 7 depicts a schematic diagram illustrating
settings utilized during the biochar manufacturing process (Cheng et al., the various modification methods of carbon nanotubes for pollutant
2021; Mitchell et al., 2015; Tan et al., 2017). For example, “Arundo removal from water and wastewater. Carbonaceous materials behave
donax L”. a species of cane that has been employed in the creation of differently depending on the method used to manufacture them, as
biochar. The removal effectiveness of sulfamethoxazole from biochar demonstrated by the elimination efficiency of carbon nanotubes, bio­
varies depending on the thermal activation conditions used in its char, and activated carbon. The ability of CNTs to remove ECs is largely
manufacture while the other parameters remain constant. Biochar determined by their surface area. While the formation of the carbon
manufactured with absence of thermal activation was capable to elim­ nanotubes is critical for surface area development and can outcome in
inate 35 percent of sulfamethoxazole, whereas biochar produced with different elimination rates for the same pollutant. For example, Ji et al.
thermal activation was only able to eliminate 16 percent (Zheng et al., (2010b) successfully eliminated tetracycline with a 92 percent removal
2013). The porosity and particle size of biochar, which is converted into rate with SWNT, but only 16 percent using MWNT while maintaining the
feedstock and can affect ECs elimination, are ascribed to the biochar’s same settings in both situations. Others have also utilized MWNT to
acid base and hydrophobic-hydrophilic properties as a result of thermal remove ECs, including amoxicillin (Teixidó et al., 2011), ciprofloxacin
activation. Like activated carbon, the feedstock acting an important (Mitchell et al., 2015) and triclosan or ibuprofen (Zheng et al., 2013)
function in biochar formation because it influences selectivity and with a elimination rate of 6.7%, >90% and 100% respectively. Addi­
treatment efficiency, which are both important factors in EC removal. In tionally, single-walled carbon nanotubes have been shown to be effec­
the case of wood feedstock, the value of sulfamethoxazole elimination tive at removing of norfloxacin at a rate of 100 percent (Peng et al.,
was in the region of 12 percent, whereas the value of “sugarcane feed­ 2012), although multi-walled carbon nanotubes removed up to 35
back” based biochar was up to 21 percent, respectively (Yao et al., percent (Yang et al., 2012). While single-walled carbon nanotubes can
2012). The biochar derived from rice straw and rice husk has been be employed to manufacture multi-walled carbon nanotubes by chem­
capable to eliminate 11.6 percent until it is treated with ical procedures (Cho et al., 2011; Ji et al., 2010a), the increased active
alkaline-produced biochar with 30 percent elimination effectiveness sites and contact zone resulting in increased removal efficiency. How­
(Liu et al., 2012). The existence of carbon, in combination with phos­ ever, because of the presence of molecular sieving processes in MWNTs,
phorus and nitrogen, has a significant impact on sorption and remedial not all of these characteristics are indicative of improved performance
efficacy. Heat and chemical treatment have both been shown to alter the (Cho et al., 2011; Zhang et al., 2011).
chemical characteristics of the final product, which in turn affects the It is recommended that additional study be undertaken in this sector
efficiency with which ECs are removed. This has been addressed from due to the small number of studies that have been conducted on the
the beginning of active carbon. On the other hand, Jeong et al. (2012) removal of ECs using CNTs in order to get experimental confirmation
investigated the elimination of tylosin by biochar made from various that is considerable in support of prior theories. In certain instances, the
materials under various heating settings and discovered that all biochar relative examination of both types of CNTs results in superior perfor­
products removed up to 10% of the tylosin. The findings are related to mance while in some circumstances both types of CNTs show altered
the chemical composition of tylosin, which contains a greater number of performance with the same pollutant (Ong et al., 2010; Tian et al.,
hydroxyl groups than sulfamethoxazole and other antibiotics. Tylosin’s 2013). Future research could focus on the use of significant nano­
chemical structure has a higher oxidation state, resulting in a higher materials with reactive properties and the sorption properties of carbon
water solubility and water-octanol partition coefficient when compared nanotubes.
to other antibiotics, resulting in decreased elimination ability. Despite
similar qualities, biochar did not perform in coupling treatment systems 5.4. Sorption of ECs onto clay minerals
similarly to activated carbon. This is due to the sort of material used in
this technology, as well as the ECs that are being targeted for removal. Clay minerals are primarily made of silica, alumina or magnesium, or
Although biochar exhibits a distinct specificity when compared to acti­ both, and water, but iron frequently substitutes for aluminum and
vated carbon, it may be able to eliminate emerging contaminants more magnesium in variable degrees, and significant amounts of potassium,
effectively than activated carbon in certain situations (Mitchell et al., sodium, and calcium are frequently present as well. The effectiveness
2015). As a result, additional research on coupled treatment systems with which a substance is treated is highly dependent on its adsorbent
that incorporate biochar’s beneficial properties is needed. characteristics. The efficiency of removal varies due to the presence of
Another major problem for investigations in the area of biochar is the varying concentrations of iron, nitrogen, and other minerals (Rahardjo
long-term viability of the manufacturing method. Agricultural waste has et al., 2011). But, depending on the clay kind, the effectiveness of
the potential to be used as a source for biochar manufacturing. But, the elimination can be enhanced through surface alteration of clay particles.
examination is essential to ensure that the waste material is not suitable Physicochemical features of surface modified clays are distinct from
for use in other purposes other than biochar production. The dearth of those of native clays (Aboudi Mana et al., 2017; Alexander et al., 2018;
understanding regarding how to keep increasing biochar production Liu, 2007), and as a result, the modified clay particles can be used as
processes is another barrier to overcome. Kilns consume a large amount valuable adsorbents to eliminate larger concentrations of emerging
of energy during the biochar synthesis process, despite the fact that it is a contaminants than native clays. The sorption ability of raw clay was
small-scale industrial process. Identification of more environmentally increased by spray drying a dispersed clay solution, and methylene blue
friendly and capable biochar fabrication processes that take carbon was removed from the surface with the assistance of sodium dodecyl

12
S. Khan et al. Environmental Research 207 (2022) 112609

Fig. 7. Schematic diagram representing different modification processes of CNTs for contaminant removal from water and wastewater (C: Carbon; CNT: Carbon
nanotube; ENVT: Environmental; Hg: Mercury; KOH: Potassium hydroxide). Reprinted from Sarkar et al. (2018), with permission of Elsevier B.V. copyright (2017).

sulfate (SDS) (Olusegun et al., 2018; Wu et al., 2010b) and Wu et al. technologies for removing emerging pollutants from aqueous solutions.
(2012) demonstrated this by utilizing montmorillonite to remove cip­ However, inadequate knowledge exists, indicating the enormous prob­
rofloxacin at a rate of 100% and 35%, respectively. In batch experi­ lem of ensuring the safety of reused water intended for human con­
ments, the reactions between the antibiotic (ciprofloxacin) and the sumption. This review assesses unwanted consequences of emerging
mineral kaolinite in a solution were studied (Li et al., 2011). Previous contaminants and summarizes the several potential remediation stra­
findings using ciprofloxacin and clay minerals have also emphasized the tegies. The elimination of emerging contaminants using a single treat­
importance of clays with increased swelling properties, as they have a ment method does not seem to be the main method that requires the
significantly greater capacity for sorption of ciprofloxacin (Jiang et al., deployment of coupling treatment methods to prevail over the short­
2013; Wang et al., 2010). To employ the adsorbent capabilities of clay in comings of the single treatment method. Despite their immense poten­
combinations with ions, this in the case of metal oxide pillared clays tial, phase change technologies for the treatment of wastewater
generates an intriguing reaction in porous support. Pore diameters of the containing EC residues remain ineffective. These techniques can still be
porous support may range between 1.49 and 3.2 nm, which is appro­ used for concentration pre-treatment and integrated progressively into
priate for catalysis within the clay. further treatments in order to effectively degrade emerging contami­
Recently, the usage of pillared clays has generated substantial in­ nants in the wastewater. Synergistic approaches to identify and build
terest due to its potential use as a semiconductor for contaminant stand-alone solutions to eliminate or degrade emerging pollutants of
degradation while rising surface area via metal oxide reactivity (Fati­ considerable environmental relevance may prove to be a significant
mah et al., 2011). This type of advanced oxidation system has been used method in the future. Numerous important disadvantages of conven­
in “Fenton-type” reactions to prevent the catalyst from impregnating the tional treatment procedures used to generate nano-scale materials can
clay mineral after the reaction and to improve the matrix using settling be solved by following or even combining the entire creation procedure
or magnetic techniques (Guz et al., 2014; Rasheed et al., 2019a). The with modification approaches. In this perspective, future studies should
experiments carried out offer promising results that may be studied to include the influential and critical components of numerous modifica­
understand the elimination mechanism and the pollutant fate. For tion procedures to acquire a better understanding. Another fascinating
example, two routes of sorption and degradation (within clay mineral) field of research in emerging pollutant degradation/elimination is the
take place during treatment of contaminants; these studies don’t clarify development of innovative materials and nanocatalysts for biological
which phase is the first. processes that adhere to a green agenda in order to design highly effi­
cient and environmentally friendly treatment procedures.
6. Concluding remarks and future perspectives
Declaration of competing interest
The elimination of harmful chemicals and their emergent derivatives
found in the environment or aquatic systems, such as dye pollutants, The authors declare that they have no known competing financial
personal care products, pesticides, polycyclic aromatic hydrocarbon- interests or personal relationships that could have appeared to influence
based ECs, dioxin- and biphenyl polychlorinated-based ECs, and phar­ the work reported in this paper.
maceuticals, has been a global environmental issue in the modern era. In
recent years, a lot of effort has gone into developing treatment

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Acknowledgements Bilal, M., Adeel, M., Rasheed, T., Zhao, Y., Iqbal, H.M.N., 2019b. Emerging contaminants
of high concern and their enzyme-assisted biodegradation – a review. Environ. Int.
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This work is supported by the Scientific Research Project of Neijiang Bilal, M., Asgher, M., Iqbal, H.M., Hu, H., Wang, W., Zhang, X., 2017a. Bio-catalytic
Normal University, China (2020WJ09). The authors would like to thank performance and dye-based industrial pollutants degradation potential of agarose-
the anonymous reviewers for their valuable comments and suggestions immobilized MnP using a Packed Bed Reactor System. Int. J. Biol. Macromol. 102,
582–590.
to improve the paper’s quality. Bilal, M., Asgher, M., Iqbal, H.M., Hu, H., Zhang, X., 2017b. Bio-based degradation of
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