Science of the Total Environment 753 (2021) 141990

Contents lists available at ScienceDirect

Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Treatment technologies for emerging contaminants in wastewater

treatment plants: A review
Prangya R. Rout a, Tian C. Zhang b, Puspendu Bhunia c, Rao Y. Surampalli b,d,⁎
a
Environmental Engineering, INHA University, Incheon, Republic of Korea
b
Department of Civil and Environmental Engineering, University of Nebraska-Lincoln, Omaha, NE 68182, USA
c
Departement of Civil Engineering, Indian Institute of Technology Bhubaneswar, India
d
Global Institute for Energy, Environment and Sustainability, Kansas, USA

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Treatment technologies for emerging

contaminants (ECs) are comprehen-
sively reviewed.
• The ECs with risk quotient, RQ > 1 have
high environmental risk potential.
• The ECs with biodegradation kinetics,
Kbio > 10 are highly biodegradable in
nature.
• ASP and MBR are effective biological
technologies for ECs removal.
• Ozonation and activated carbon treat-
ment are best performing tertiary
treatments.

a r t i c l e i n f o a b s t r a c t

Article history: The “emerging contaminants” (ECs) are predominantly unregulated anthropogenic chemicals that occur in air,
Received 31 May 2020 soil, water, food, and human/animal tissues in trace concentrations. The ECs are persistent in the environment,
Received in revised form 6 August 2020 capable of perturbing the physiology of target receptors and, therefore, are regarded as contaminants of emerging
Accepted 24 August 2020
environmental concerns in recent years. The prominent classes of ECs include pharmaceuticals and personal care
Available online xxxx
products (PCPs), surfactants, plasticizers, pesticides, fire retardants, and nanomaterials. Some of the ECs with
Editor: Huu Hao Ngo harmful effects on endocrine systems have been recognized as endocrine disrupting chemicals (EDCs). Since
the 1990s intensive research has been done covering environmental occurrence, fate, ecological effects, and
Keywords: treatment technologies of ECs. However, a comprehensive summary of the EC removal techniques, particularly
Endocrine disrupting chemicals in wastewater treatment plants (WWTPs) are limited. Though the WWTPs are inefficient when it comes to
Pharmaceuticals ECs removal, they act as primary barriers against the spread of ECs. Therefore, this paper reviews the treatment
Personal care products technologies currently engaged for ECs removal in WWTPs for further possible upgrades of the existing designs.
Adsorption Results of this review indicate that the fate and distribution of ECs can be approximately estimated based on
Membrane bioreactors
physicochemical properties like octanol-water partitioning coefficient (e.g., log KOW > 4, maximum sorption po-
Ozonation
tential) and solid-water distribution coefficient [e.g., Kd < 300–500 L/kg MLSS (mixed liquor suspended solids),
insignificant sorption into sludge]. Biodegradation potential of ECs can be predicted from biodegradation

⁎ Corresponding author at: Department of Civil and Environmental Engineering, University of Nebraska-Lincoln, Omaha, NE 68182, USA.
E-mail address: Surampalli.Rao@GIEES.Com (R.Y. Surampalli).

https://doi.org/10.1016/j.scitotenv.2020.141990
0048-9697/© 2020 Elsevier B.V. All rights reserved.
2 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990

constant values (e.g., Kbio < 0.01 = low biodegradation and >10 = high biodegradation). In WWTPs, the EC re-
moval efficiency varies in the range of 20–50%, 30–70%, and >90% during the primary, secondary, and tertiary
treatment steps, respectively. Tertiary treatment technologies are considered as the most suitable alternatives
for ECs treatment, but complete ECs removal is yet to be achieved. Further advancements in the treatment tech-
nologies will unquestionably be necessary in the future.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction mass spectrometry (LC/MS) (Kolpin et al., 2002). As shown in Fig. 1,

the lag was 27 years between the time for pharmaceuticals being first
In recent decades, the occurrence of a multitude of newly identified detected in surface water using GC/MS (1975) and the time for the
compounds of anthropogenic or natural origin in the aquatic environ- widespread occurrence of ECs being realized through large scale water
ment has become a global issue of increasing environmental concern. quality survey of US streams using LC/MS (2002). Further improvement
These contaminants are mostly organic in nature and typically occur in mass accuracy and resolving power of quadrupole time of flight (Q-
in trace concentrations in the range from parts per trillion (ppt or TOF) MS and orbitrap MS has accelerated ECs related research exponen-
ng/L) to parts per billion (ppb or μg/L) (Rodriguez-Narvaez et al., tially in recent years. The ECs will continue to be an enduring target of
2017). These compounds are named as “emerging contaminants the scientific community due to ever increasing the synthesis of a
(ECs)” (Philip et al., 2018 Díaz-Garduño et al., 2017), micropollutants large variety of new chemicals in proportion to the industrial develop-
(MPs), emerging pollutants (EPs), contaminants of emerging concern ments and technological advancements.
(CEC), or trace organic compounds (TrOCs) by different research groups The widespread existence of ECs in receiving aquatic environments
(Luo et al., 2014 Das et al., 2017 Gogoi et al., 2018 Rizzo et al., 2019 is a growing concern because of their undesired synergistic effects.
Grandclément et al., 2017). United States Geological Survey defined Short term toxicity studies revealed that the ECs don't have either
ECs as “any chemical of synthetic or natural origin or any microorgan- acute toxic effects or suspected effects on the receiving environments
ism that is not commonly monitored in the environment but has the po- because of their low concentration; therefore, they are rarely regulated
tential to cause adverse ecological and/or human health effects” (USGS, unlike conventional pollutants (Pesqueira et al., 2020 Rodriguez-
2017). In effect, microbial contaminants in the environment, including Narvaez et al., 2017). However, constant release of ECs, their persistent
antibacterial drugs mediated antibiotic resistance genes (ARGs)/bacte- nature, tendency to form complex, and bioaccumulation potential can
ria, are also considered as ECs and more specifically can be termed as lead to serious chronic effects on aquatic biota, human and animal
emerging microbial contaminants (Petrie et al., 2015 Philip et al., 2018 health, and the environment on long term exposure (Barbosa et al.,
Hartmann et al., 2020). ARGs can further be transferred among micro- 2016 Pesqueira et al., 2020). The common adverse environmental ef-
bial populations through horizontal gene transfer (HGT) that is the fects of selected ECs, along with their general functions, are listed in
movement of genetic materials between unicellular and/or multicellu- Table 1. The assessment of the potential risk associated with ECs is
lar organisms. Therefore, mitigation strategies are vital to prevent the done based on risk quotient (RQ). The predicted no effect concentra-
widespread dissemination of ARGs. Waddlia chondrophila, sapoviruses, tions (PNECs) of ECs are compared with the predicted environmental
tetracycline ARGs [tet(O), tet(S), and sulfonamide ARGs (sul(I), sul concentrations (PEC) to obtain the RQ value as per the following equa-
(II))] are few examples of emerging microbial contaminants tion:
(Hartmann et al., 2020 Pruden et al., 2006). The United States Environ-
mental Protection Agency (USEPA) defines ECs as considerably new PEC
RQ ¼ ð1Þ
compounds that have harmful (but yet fully understood) impacts on PNEC
the health of living beings and the environment (de Oliveira et al.,
2019). where PEC is an indication of the expected concentration of ECs in the
The existences of these chemical compounds in environmental environment, which can be estimated from the available literature on
media are not a new phenomenon and can be dated back to environmental concentration, persistence, fate, and transport of ECs.
2000 years ago with the emergence of the oldest global contaminant, Likewise, PNEC signifies the sensitivity of a specific organism, which
lead due to over exploitation of lead mines by Romans and Greeks means the concentration of ECs at which no harmful effect is expected
(Sauvé and Desrosiers, 2014). Subsequently, the trend gradually sweeps to occur to a living being exposed to that ECs (Peake et al., 2016). The
through the traditional contaminants to the present day nanomaterials, PNEC is usually calculated from LC50 values (the concentration lethal
pharmaceuticals, personal care products, etc. The first documented to 50% of organisms) or EC50 values (the concentration at which the
awareness of emerging contaminants should probably be attributed to toxic effect of a compound on an organism in an aquatic environment
the “Silent Spring” the 1962 book by Rachel Carson that advocated the is halfway between non-toxic and maximum toxicity). In general, if
link between widespread usage of dichlorodiphenyltrichloroethane the exposure level (PEC) is higher than the sensitivity of the species
(DDT) and environmental hazards (Carson, 2002 Sauvé and (PNEC), the RQ will be >1, indicating the high environmental risks.
Desrosiers, 2014). However, the environmental occurrence and detec- Based on RQ values, the risk levels of ECs can be ranked as negligible risk
tion of ECs have been investigated extensively only in the last two de- (RQ < 0.01), low risk (0.01 > RQ < 0.1), medium risk (0.1 > RQ < 1),
cades. This lag in the detection of ECs can be attributed to the slow and high risk (RQ > 1) (Díaz-Garduño et al., 2017). ECs like diclofenac,
development of sensitive analytical techniques and/or new detection nicotine, codeine, sulfamithoxazole, etc. with RQ > 1 are considered as
methods capable of detecting a very low concentration of ECs in the en- environmental risks (Archer et al., 2017). The major deleterious impacts
vironmental samples (Noguera-Oviedo and Aga, 2016). Fig. 1 highlights of ECs include a reduction in macro-invertebrate diversity in rivers,
the significant milestones of ECs research emphasizing instrument de- harmful effects on the fish population, freshwater mussels, human and
velopment for environmental sample analysis. Gas chromatography wildlife endocrine systems, and carcinogenic effects (Mohapatra and
with mass spectrometry (GC/MS) is the conventional method used for Kirpalani, 2019 Rodriguez-Narvaez et al., 2017).
ECs analysis; however, the majority of the ECs are not responsive to The ECs that affect endocrine systems are termed as endocrine
GC/MS techniques. Therefore, the ubiquitous nature of ECs in the envi- disrupting chemicals/compounds (EDCs), and the European Union de-
ronment is realized only after introducing liquid chromatography with fines them as compounds that may interfere with the physiological
 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990 3

Fig. 1. Highlights of major events in ECs research (conceptualized from Noguera-Oviedo and Aga, 2016; Sauvé and Desrosiers, 2014). DBPs (disinfection byproducts), DecaBDE
(decabromodiphenyl ether), EDCs (endocrine disrupting chemicals), ESI (electrospray ionization), GC (gas chromatography), LC (liquid chromatography), MS (mass spectrometry),
PBDEs (polybrominated diphenyl ethers), PFASs (Perfluorinated alkylated substances), Q-TOF (quadrupole time of flight).

hormone systems of human beings affecting the uterus and having effective removal of ECs (Pesqueira et al., 2020). Nevertheless, ozona-
damaging effects on the future generations (Commission European, tion may result in oxidation byproducts formation; adsorption by acti-
2016 de Oliveira et al., 2019). EDCs are a group of highly heterogeneous vated carbon is less effective in inactivating bacteria; and membrane
chemical molecules, not limited to polychlorinated biphenyls (PCBs), filtration faces challenges in concentrate disposal in addition to high op-
phthalates, bisphenol A (BPA), polybrominated diphenyl ethers erational energy demand (Rizzo et al., 2019). Advanced treatment tech-
(PBDE), diethylstilbestrol (DES), ethinyl estradiol (EE), dichlorodiphe- nologies like advanced oxidation processes, constructed wetlands,
nyltrichloroethane (DDT), organophosphate insecticides (OPs), genis- bioelectrical systems, enzymatic treatment, etc., have been proposed
tein (GEN), pharmaceutical agents, etc. (Frye et al., 2012). Depending in the past few years.
on the time and dose of exposure, the ECs can cause male and female Despite the availability of these treatment technologies, the removal
sexual disorders including polycystic ovaries, reduced male fertility, efficiency of most of the employed technologies for ECs is not satisfac-
longer time to conception, higher miscarriage rates, altering both male tory, depending mainly on the physico-chemical properties of the ECs
and female gonad development, prostate, testicular, and breast cancers and treatment conditions. It has been reported that even conventional
(Stackelberg et al., 2004 de Oliveira et al., 2019). Prolonged exposure to wastewater treatment plants (WWTPs) are able to remove efficiently
estrogen in a low concentration in the aquatic environment leads to the some ECs, although they are not designed to eliminate ECs at low con-
feminization of male fish (shift in species trait), whereas high centrations (Alvarino et al., 2018). Therefore, the WWTPs act as primary
estrogenicity results in the increased fish mortality rate (Gross- barriers against the spread of ECs, and upgrading the treatment pro-
Sorokin et al., 2006 Jukosky et al., 2008). cesses of conventional WWTPs might further minimize the environ-
Antibiotics exposure leads to the development of antibiotic resistant mental release of ECs. Many countries across the globe are planning to
bacterial strains/genes, whereas human exposure to pesticides can re- upgrade multiple WWTPs by employing advanced treatment technolo-
sult in cancer and cognitive effects (Grenni et al., 2018 Kim et al., gies to comply with ECs removal goals to protect the environment
2017). Likewise, tetracycline with a concentration of 10–100 μg/L (Roccaro, 2018 Pesqueira et al., 2020). For example, advanced oxidation
caused low populations of algae, bacteria, and nematodes in artificial processes (AOPs) are the most investigated advanced treatment pro-
streams, whereas significant decline in vulture population in Asia was cesses for ECs removal in the last few years, but they do not find the ap-
due to the presence of diclofenac in their food that induces visceral plication at full scale yet, thus, further discussions of AOPs are not
gout, renal failure and death (Quinlan et al., 2011 Oaks et al., 2004 reviewed here (Rizzo et al., 2019). Therefore, as a first approach to con-
Tiwari et al., 2017). The environmental persistence of the ECs, alone or sidering upgradation of WWTPs, the existing ECs removal technologies
in mixtures, will have irreparable harmful effects, presumably leading in WWTPs must be well understood and assessed in order to determine
to the extinction of some ecosystems (de Oliveira et al., 2019). There- the best fit alternative both economically and environmentally. How-
fore, in this context, it is essential to set stricter discharge limits for ever, a comprehensive summary of the EC removal techniques is lim-
ECs and develop advanced technologies for ECs removal from the envi- ited. Therefore, this paper aims to undertake a systematic review of
ronmental samples. the treatment technologies currently engaged for ECs removal in
Many technologies for ECs removal have been developed, and they WWTPs. The paper starts with an overview of the classification, sources,
can be categorized broadly into natural attenuation, conventional, and occurrence and fate/transport of ECs in the environment (and the detail
advanced treatment processes. All the applicable physical, chemical, or information can be referred elsewhere, such as Bhandari et al. (2009),
biological natural attenuation processes like dilution, volatilization, Luo et al. (2014), Archer et al. (2017), K'oreje et al. (2020), followed
photolysis, sorption, biodegradation, etc., are cost effective and simple by a critical review of the treatment techniques of ECs in WWTPs. The
processes. However, processes like volatilization have less efficiency; occurrences of ECs in the particulate phase (sludge) are briefly
suspended particles interrupt the photocatalysis efficiency; and EC ac- discussed since most of the published literature has focused more on
cumulations enhanced in the sorption process (Barbosa et al., 2016). the ECs occurrence in the dissolved phase (wastewater) over the partic-
Conventional treatment technologies, such as membrane filtration, acti- ulate phase. The treatment techniques are discussed briefly, emphasiz-
vated carbon mediated adsorption, ozonation, etc., have also exhibited ing the principle, their performance efficiency, advantages, and
4 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990

Table 1 2. Classification, sources, occurrence and fate/transport of ECs

General functions and adverse environmental effects of selected ECs.

Emerging contaminants Function Adverse effects Table 2 summarizes a general classification of ECs and their major
Antibiotics Antimicrobial substances Induce antibiotic
sources. Out of the extensive list of ECs detected in environmental sam-
(clarithromycin, that stop infection by resistance in microbial ples, around 70% are pharmaceutically active compounds (PhACs) and
penicillin, killing or inhibiting strains, alter microbial personal care products (PCPs), and 30% are industrial and agricultural
sulfonamides, growth of bacteria. community structure, and compounds (Das et al., 2017). For example, to date, more than 200
roxithromycin, cause low population of
PhACs have been reported globally in river waters with a maximum re-
tetracycline) algae, bacteria,
nematodes, etc. ported concentration of 6 mg/L for ciprofloxacin antibiotic (Petrie et al.,
Fragrances (galaxolide, Used as a fragrance Toxic to aquatic 2015 Hughes et al., 2013). Likewise, tamoxifen, an anti-cancer drug, was
musk xylene, musk ingredient in a wide range organisms, cause detected in the range of 25–38 ng/L in river waters (Ferrando-Climent
ketone) of consumer products oxidation stress to gold et al., 2014). Jones et al. (2001) reported that the environmental con-
including perfumes, fish, carcinogenic to
cosmetics, shampoos, etc. rodents, may damage the
centrations of antibiotics, hormones, antidepressants, lipid regulators,
human nervous system analgesic compounds, and chemotherapy drugs range from 0.04 to
Preservatives (methyl Prevent microbial Responsible for weak 6.3 μg/L. On the other hand, high usage chemicals like sunscreen agents
paraben, decomposition and used estrogenic activity and preservatives are often observed at concentration ranges more than
2-phenoxyethanol) in cosmetics, toiletries,
1000 ng/L (Petrie et al., 2015). For example, 4-benzophenone, the sun-
etc., as preservative
ingredients. screen agent, has been detected in environmental samples in the
Fire retardants Used as flame retardant Affect brain and nervous range of 3597–5790 ng/L (Kasprzyk-Hordern et al., 2009). However,
(polybrominated chemicals in paints, system, hormone activity, for a number of these ECs, their EC50 values are reported to be
diphenyl ethers or plastics, televisions, reproduction and fertility. <1 mg/L (Petrie et al., 2015). The contaminants are categorized as
(PBDEs)) building materials, etc., to
harmful to aquatic organisms for their EC50 values of 10–100 mg/L,
make them difficult to
burn. toxic for that of 1–10 mg/L, and very toxic for that <1 mg/L (Cleuvers,
Endocrine disrupting Group of chemicals used Interfere with endocrine 2003).
chemicals (phthalates, as plastics, plasticizers, system, estrogenic effects ECs can enter the aquatic and subsurface environment through di-
bisphenol) industrial in rats, feminising side
versified sources (Table 2), which can be classified into five categories:
solvents/lubricants, etc. effects in men, birth
defects and
domestic wastewater, effluents from industry, hospital, livestock farm-
developmental delays. ing, and agricultural activities (Fig. 2). Among the various sources, do-
Nonsteroidal Reduce pain, fever and Increased risk of mestic discharge is one of the major sources of PhACs and PCPs into
anti-inflammatory inflammation. gastrointestinal ulcers, the environment. For example, medicines consumed by humans are
drugs (diclofenac, kidney diseases, gill
metabolized in the body and excreted via urines and feces and subse-
ibuprofen) alterations of rainbow
trout. quently discharged to the environment through wastewater streams.
Lipid regulators Regulation of levels of Inhibition of Likewise, PCPs like shampoos, sunscreen lotions, toothpaste, etc. are
(clorfibric acid, triglycerides and bioluminescence, growth discharged to the environment through the washing activities of
gemfibrozil) cholesterol in blood inhibition of microalgae.
human beings (Yang et al., 2017). The effluents of the manufacturing
Beta-blockers (atenolol, Manage abnormal heart Affect reproduction and
metoprolol) rhythms by inhibiting the growth of fishes, inhibit
units of pharmaceuticals, PCPs, biocides, and other chemicals are
hormone adrenalin and receptor discharge in the major contributors of ECs to the environments (Barbosa et al., 2016).
noradrenalin. gills, impact breeding As another dominant contributor of ECs, the hospitals' effluents contain
cycles and activity drug conjugates, antibiotic resistance bacteria/genes, pharmaceutical
rhythms in trout.
metabolites, radioactive elements, etc. (Tiwari et al., 2017). The runoff
Anticonvulsants Treat mood disorders and Oxidation stress of
(carbamazepine) epileptic seizures rainbow trout, affects from livestock farming and agricultural activities are the other impor-
central nervous system. tant sources of ECs, particularly in the form of steroid hormones and
Hormones (estrone, Regulation of metabolism, Affect reproduction and pesticides used for enhanced productivity (Barbosa et al., 2016). The
testosterone) homeostasis, control of fertility, masculinization
EC contribution from these sources depends on the biocides/pesticides
the sexual development. of females, feminization of
males, reduced fertility in
used, characteristics of the surface water bodies, and climatic conditions
fish. (Bermúdez-Couso et al., 2013). Other contributors of ECs to the environ-
Poly aromatic Used in manufacture of Carcinogenic effect, cardio ment include landfill leaching, irrigation using reclaimed water, aqua-
hydrocarbons plastics, pesticides, dyes, vascular diseases, poor culture discharge, leakage from sewage treatment facilities, etc. (Yang
(anthracene, pyrene) etc. fetal development.
et al., 2017).
Perfluorinated alkylated Used in emulsion Thyroid disease, liver
substances polymerization, polishes, damage, kidney cancer, After entering the environment, ECs further migrate to the different
(perfluorooctanoic paints, and coatings reduced response to aquatic environments following miscellaneous pathways (Fig. 2). A
acid) vaccines, developmental large variation in concentrations of ECs in different aquatic environ-
effects on unborn child. ments has been observed, which are essentially due to a number of fac-
Nano materials Used in a variety of, Affects respiratory
(nanoparticles, manufacturing processes, systems, wild life and
tors like dilution, environmental persistency, treatment efficiency, etc.
nanocomposites) products and healthcares. environmental toxicity (Luo et al., 2014). Usually, the occurrence of the ECs in the aqueous en-
Viable but nonculturable Significant implications in Affect gastro-intestinal vironments was reported in different categories like wastewater or
microbes Yersinia bioremediation and systems, immune system, wastewater treatment plants (WWTPs), sewage sludge, surface water,
pestis, Vibrio cholerae) pathogenesis. toxic to environment and
groundwater and drinking water (Luo et al., 2014 Yang et al., 2017
wild lives,
K'oreje et al., 2020). The concentrations of ECs in wastewater treatment
plants/wastewater are dependent on their usage patterns. For example,
considering an intra-day variation, a peak in antibiotic load was ob-
served in wastewater treatment plant between 7:00 to 9:00 am due to
the accumulation of ingested drugs in urine during sleep (Coutu et al.,
limitations. Moreover, the identified gaps are detailed, and future re- 2013). Likewise, in view of inter-day variation, an elevated level of me-
search opportunities to provide more suitable treatment solutions for tabolites of cocaine was reported in the wastewater in European coun-
ECs are discussed. tries during weekends due to the recreational use of these compounds.
 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990 5

Table 2
General classification and major sources of ECs.

Class Important sub-class Representative ECs Major sources

Pharmaceutically Antibiotics, Antidepressant, Nonsteroidal anti-inflammatory Ciprofloxacin, Diazepam, Diclofenac, Pharmaceutical industry effluent, Hospital
active drugs (NSAID), Lipid regulators, Hormones, Anticonvulsants Clorfibric acid, Testosterone, effluent, Domestic wastewater, Effluent from
compounds and, Beta-blockers Carbamazepine, Metoprolol livestock farms and aqua culture
(PhACs)
Personal care Fragrances, Sunscreen agents/UV filters, and Insect Galaxolide, 4-benzophenone, N, N Surface water, WWTP effluent, and Landfill
products (PCPs) repellants ′-diethyltoluamide (DEET) leachate
Industrial Fire retardants and Plasticizers Tris (1-chloro-2-propyl) phosphate Industrial effluent and Domestic wastewater
chemicals (TCPP) and Dimethyl adipate (DMAD)
Endocrine Xenohormone, Bisphenol, and Phthalates Xenoestrogen, Bisphenol A (BPA), and Surface water, Drinking water, Secondary sludge,
disrupting Dioctyl phthalate (DOP) Soil, and Sediments
chemicals
(EDCs)
Biocides Fungicide, Herbicide and Molluscicide Epoxiconazole,.Butachlor, and Agricultural runoff, Aquaculture effluent, and
Metaldehyde Surface water
Regulated Poly aromatic hydrocarbons (PAHs) and Pesticides Phenanthrene and Chlorpyrifos Sewage treatment plants, Agricultural runoffs,
compounds Surface water, Soils, and Sediments
(RCs)
Surfactants Ionic surfactants and nonionic surfactants Sodium lauryl sulfate (SLS) and Domestic wastewater and Industrial effluents
Tweens (Polysorbates)
Artificial Aspartame, Saccharin and, Sucralose – Sewage treatment plant effluent, Wastewater,
Sweeteners and Landfill leachate
Perfluorinated Perfluorosulfonic acids and Perfluorocarboxylic acids Perfluorooctanesulfonate (PFOS) and Surface water, Ground water, Wastewater, and
alkylated Perfluorooctanoic acid (PFOA) Sediments
substances
(PFASs)

Similarly, seasonal variability of ECs in wastewater includes enhanced reported concentrations of 3.73–603 and 50 μg/L, respectively (Luo
detection of sunscreen agents in wastewater during summer and of et al., 2014 Santos et al., 2009 Zhou et al., 2010). So far, the release of
pholcodine (a cough syrup agent) in winter (Petrie et al., 2015). Most WWTP effluent into the surface water is considered as the primary
of the ECs occurred in WWTPs in the concentration range between 0.1 cause for the occurrence of ECs in surface water (Kasprzyk-Hordern
and 10 μg/L, with some exceptions like ibuprofen and caffeine with et al., 2009).

Application

Hospital/Commercial Livestock farming

Industry Domestic
Agriculture

WWTP
Direct discharge
Direct discharge Sludge
Effluent

Surface
Landfill Soil
Drinking water water
Runoff

Bank filtration
Leaching Percolation
Water treatment
Ground water
plant

Pathways of ECs in the environment Direct discharge of ECs from sources

Fig. 2. Major sources and pathways of ECs in the aquatic and subsurface environments.
6 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990

In surface water, due to the dilution of ECs, the ECs' concentrations contamination (Barbosa et al., 2016 Petrie et al., 2015). Consequently,
are at least one order of magnitude lower than the WWTP effluent levels the persistent ECs in the sludge can contaminate soil and groundwater.
(Gros et al., 2007). Rainfall helps in further dilution of ECs in surface Therefore, the information on the occurrence and distribution of ECs in
water in one way, but, in the other way, may result in high concentra- the sludge is important for planning the sludge management strategy.
tions of ECs through chemical leaching from pavement materials, build- Relatively high concentrations of ECs occurrence have been reported
ing and roof paints, sewer overflow, and increased runoff due to flash in earlier studies compared to their occurrence in wastewater. The max-
floods (Sakamoto et al., 2007 Jungnickel et al., 2008 K'oreje et al., imum occurrence concentrations of some selected ECs both in WWTPs
2020). The most common ECs in surface water are NSAIDs, triclosan, effluent and sludge are presented in Fig. 3. The concentrations of the se-
sulfamethoxazole, and carbamazepine. Like wastewater, ibuprofen lected ECs in sludge ranged from 0 (below method detection limit) to
and caffeine also detected at high levels in surface water with reported approximately 5000 ng/g dry weight of sludge. The concentrations of
maximum concentrations of 36.8 and 1121.4 μg/L, respectively. How- ECs in sludge were dependent on their usage patterns, and physico-
ever, caffeine was also detected at relatively high concentrations chemical properties like hydrophobicity and ionization state (Tran
(1813 ng/L) in Taiwan, whereas 2704 ng/L of nonylphenol was reported et al., 2018). For example, hydrophobic ECs, like miconazole and
in a Greek river (Luo et al., 2014). Similarly, the concentrations of pesti- bisphenol A were found in higher concentrations in sludge due to
cides (e.g., insecticides, herbicides, and fungicides) reported in African their tendency to partitioned onto particulate phase whereas, ECs like
surface waters are in the ranges of 0.06 ng/L–69 μg/L, 0.2 ng/L– ciprofloxacin (fluoroquinolones) gets adsorbed onto sludge via electro-
14 μg/L, and 0.1 ng/L–9 μg/L, respectively (K'oreje et al., 2020). static interaction as it exists as a zwitterion under environmental pH
Unlike surface water, the occurrence and concentrations of ECs are (6–8) (Tran et al., 2018). Likewise, higher concentrations of ibuprofen
lower in groundwater. Landfill leachate, bank filtration, percolation from are due to hydrolysis of its conjugate, and anaerobic digestion of sludge
agricultural land, groundwater recharge using reclaimed water, and seep- was found to be effective in reducing the concentration of ibuprofen and
age of sewer systems are main routes of EC pollution of groundwater other most studied ECs like ketoprofen, ethinylestradiol, carbamaze-
(Stepien et al., 2013 Luo et al., 2014). The octanol-water partitioning coef- pine, etc. (Martín et al., 2012).
ficient (KOW) that signifies the hydrophobic partitioning of the ECs plays a Once in the environmenta, ECs go through multiple natural attenua-
vital role in deciding the level of groundwater contamination since soil is tion processes, including biodegradation/transformation, photolysis,
the major transmission pathway of ECs to the groundwater. In general, adsorption onto sediments or suspended particles, dispersion, etc.,
logKOW < 2.5 signifies high hydrophilic mobility; 2.5 < logKOW < 4 which are helpful in reducing ECs concentrations in surface water (Pal
means medium mobility; and logKOW > 4 indicates low mobility/high re- et al., 2010). The conventional WWTPs are devoid of effective treatment
tention in soil matrix (Rogers, 1996). For example, trimethoprim with mechanisms of ECs entering the WWTPs. Thus, the partially degraded or
logKOW < 1.5 is more likely to occur in groundwater as compared to tri- transformed or unchanged ECs enter into the aquatic environments
closan with logKOW > 4 mostly retained in the soil matrix (Dougherty through the post treatment discharge of the WWTP effluent and sludge
et al., 2010 Petrie et al., 2015). Like surface water, NASIDs, caffeine, sulfa- (Pesqueira et al., 2020 Luo et al., 2014). The reuse of treated wastewater
methoxazole, and carbamazepine are also commonly observed in in agricultural practices further releases the ECs to the soils, leading to
groundwater, but most of the compounds were detected at less than the subsequent uptake of the ECs by the agricultural crops (Paz et al.,
100 ng/L (a level comparable to the PNECs), and therefore, without signif- 2016). As the environmental compartments like surface water, soil,
icant environmental impacts (Luo et al., 2014). However, with some ex- and groundwater are interconnected, the presence of ECs in any of
ceptions, considerably high concentrations (in the same order of these compartments may result in a cumulative negative impact on
magnitude as in surface water) of paracetamol (18 μg/L) and nevirapine the whole environment (Daughton, 2010). Therefore, WWTPs are con-
(1.6 μg/L) were reported in groundwater of some South African countries sidered as one of the prominent anthropogenic sources emitting ECs
(Olaitan et al., 2017 K'oreje et al., 2016). Likewise, high concentrated ste- into the environment along with industrial discharges, landfill leach-
roid hormones (2–3 orders of magnitude higher than the PNEC) were de- ates, agricultural runoffs, hospital effluents, aquaculture effluents, etc.
tected in groundwater samples at a US land application site (Rizzo et al., 2019 Barbosa et al., 2016). The inability to appropriately
(Karnjanapiboonwong et al., 2011). But normally, concentrations of ECs manage ECs by identifying proper treatment technologies risks the op-
detected in groundwater are no less than one order of magnitude lower portunity of sustainable reuse of treated wastewater and sludge.
as compared to surface water (K'oreje et al., 2020).
In the case of drinking water, most of the ECs were below the detec- 3. Fate and removal of ECs in WWTPs
tion limit; therefore, limited publications are available (Vulliet et al.,
2011 Kleywegt et al., 2011). The treatment technologies that the drink- Conventional WWTPs are the standard technologies to remove a
ing water undergoes might have a significant role in keeping the ECs wide range of pollutants including suspended and colloidal particulates,
level below the detection limit in the drinking water. However, the oc- dissolved organics, nutrients and pathogens from wastewater; how-
currence of ECs in drinking water depends on the water sources and ever, they are not designed specifically for efficient removal of the ECs
seasonal variations (Luo et al., 2014). Like groundwater, most of the (Rout et al., 2016 Tran et al., 2018). The removal efficiency of ECs varies
ECs detected in drinking water are below 100 ng/L concentrations greatly depending on the persistence of ECs, their physicochemical
with the exceptions of nonylphenol (100 ng/L) and carbamazepine characteristics, employed treatment technologies, and operating/envi-
(600 ng/L), though the levels are lower than the corresponding PNEC ronmental conditions. WWTPs generally employ a primary, a secondary
values of 330 and 25,000 ng/L (Kleywegt et al., 2011). The majority of and occasionally tertiary treatment steps. Although the primary treat-
the ECs of drinking water occurrence are all at safe levels. However, ment steps are intended for removing suspended and colloidal solids,
owing to the probable adverse effects of synergism and transformation ECs are also removed to some extent, mainly via sorption onto the pri-
by-products of the ECs, the safety of the drinking water needs to be mary sludge, as depicted in Fig. 4 (Luo et al., 2014 Tran et al., 2018).
under routine monitoring and examination (Luo et al., 2014). The secondary treatment step aims at removing organics or nutrients
Contrary to the dissolved phase, the occurrence of ECs in particulate through biological degradations. In this stage, the ECs are subjected to
phases like sludge (biosolids) has been rarely reported in literature various processes like biodegradation, sorption, dispersion, dilution,
probably due to the matrix complexity of the sewage sludge/treated photodegradation, and volatilization, but the dominant mechanisms of
sludge and due to lack of sensitive analytical techniques to detect ECs EC removal are biotransformation or biodegradation and sorption (Luo
in sludge matrix (Tran et al., 2018). Agricultural application of sewage et al., 2014 Barbosa et al., 2016). As sorption is a common phenomenon
sludge as fertilizer is a common practice, and there is no legislation to both in primary and secondary treatment steps, the mechanism is
control the use of sludge on agricultural land with respect to ECs depicted in Fig. 4, whereas other dominant mechanisms are
 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990 7

Concentration in WWTPs effluent (ng/L) Maximum concentration in sludge (ng/g)

Concentration of ECs in WWTPs effluet (ng/L)

1000 6000

900

Concentration of ECs in sludge (ng/g)

5000
800

700
4000
600

500 3000

400
2000
300

200
1000
100

0 0

Emerging Contaminants (ECs)

Fig. 3. Maximum occurrence concentrations of selected ECs in WWTPs effluent and sludge. Percentage errors of data are presented by error bars. (Detailed data complied in Table 3).

demonstrated in the subsequent figures. Similarly, the tertiary treat- et al., 2017). On the other hand, there are also cases of negative removal
ment steps meant for the removal of nutrients, suspended solids and of ECs in WWTPs where the effluent concentrations of some ECs after
pathogens are reported to exhibit significant EC removal efficiency, par- treatment surpass their influent concentrations. This can be explained
ticularly the recalcitrant ones via ozonation-like conventional oxidation by the fact that most of the ECs are excreted via feces and urine as a mix-
processes (Rout et al., 2017 Ahmed et al., 2017). It is reported that the EC ture of parent chemicals and conjugates. The conjugates can revert back
removal efficiency during the primary treatment varies in the range of to its parent compounds through enzymatic cleavage during biological
20–50%, whereas comparatively better removal efficiency in the range treatment, thereby resulting in an increased concentration of the con-
of 30–70% is achieved in the secondary treatment processes (Tiwari cerned ECs. For example, the excreted conjugate compound,

Primary treatment Secondary treatment Tertiary treatment

Influent 20-50% 30-70% > 90%

100% ECs EC removal EC removal EC removal

Sedimentation Photodegradation Activated carbon

ECs removal Coagulation based adsorption
mechanisms Volatilization
Sorption Sorption Oxidation
Biodegradation

Sludge particle (-ve)

ECs Electrostatic repulsion
Dominant mechanisms
Electrostatic attraction
(+ve)
Hydrophobic interaction
Reversible adsorption
Adsorption Absorption

Mechanism of sorption of ECs to primary/secondary sludge

Fig. 4. Outline of ECs removal mechanism in a typical wastewater treatment plant.

8 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990

sulfamethoxazole-glucuronide, can be reverted to the parent com- drug acyclovir under ozonation generates a more toxic oxidation
pound, sulfamethoxazole, after the enzymatic cleavage of the glucu- product carboxy-acyclovir (Schlüter-Vorberg et al., 2015). On further
ronic acid. Furthermore, the excreted compound, acetyl- oxidation, carboxy-acyclovir transforms into N-(4-carbamoyl-2-imino-
sulfamethoxazole, after undergoing enzymatic deacetylation (loss of 5-oxoimidazolidin) formamido-N-methoxyacetic acid (COFA). Acyclo-
acetyl group), can also be converted to sulfamethoxazole as depicted vir is nontoxic to both Daphnia magna and green algae, whereas
in Fig. 5a (Noguera-Oviedo and Aga, 2016). Similarly, the deconjugation carboxy-acyclovir is toxic to Daphnia magna and COFA is toxic
of diclofenac acyl glucuronides (conjugate of diclofenac with glucuronic to green algae (Noguera-Oviedo and Aga, 2016) as shown in Fig. 5b.
acid) during biological wastewater treatment resulted in higher con- Similarly, incomplete mineralization of carbamazepine via both the ad-
centrations of diclofenac in effluent than that of the influent (Osorio vanced oxidation process and fungal biodegradation generated acridine,
et al., 2014 Tran et al., 2018). ECs like macrolide, an antibiotic could be which is more toxic and persistent than the parent compound carba-
enclosed in fecal particles and excreted with feces. Subsequently, the mazepine (Fig. 5c and d).
ECs are released from the particulate matter during wastewater treat-
ment, resulting in an increased effluent concentration of the ECs (Kim
et al., 2014 Barbosa et al., 2016). Moreover, transformation products of 3.1. Effect of primary treatment technologies on ECs removal
ECs (by biological or chemical transformation) or disinfection
byproducts of ECs (by reacting with disinfection reagents like chlorine, The physicochemical process, sorption is the principal treatment tech-
ozone, etc.) may sometimes result in more toxic and persistent variants nologies of ECs under the primary treatment category since the efficien-
than their parent compounds (Gogoi et al., 2018). For example, antiviral cies for ECs by other physical processes like sedimentation and

Fig. 5. (a) Conjugation-deconjugation reaction of sulfamethoxazole, toxic transformation of (b) acyclovir by oxidation, (c) carabamazepine by advanced oxidation, and (d) carabamazepine
by microbial degradation.
 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990 9

flocculation are reported to be less than 10% (Ahmed et al., 2017). The whereas the other mechanisms like photodegradation and volatiliza-
term sorption represents both the mechanisms of absorption of ECs tion have minimal impacts on EC removal efficiency (Kim et al., 2014).
onto the lipid fraction of the primary sludge through hydrophobic interac- Photodegradation-mediated EC removal is insignificant during second-
tions and adsorption of ECs on to the surface of sludge particles mostly via ary treatment due to low light exposure relative to the wastewater
electrostatic interactions as demonstrated in Fig. 5 (Alvarino et al., 2018). treatment volume and blockage of sunlight by highly-concentrated par-
The sorption of ECs is dependent on the physicochemical properties of ticulate matters present in wastewater (Norvill et al., 2016). Similarly,
ECs, characteristics of the sorption media, and operating environmental ECs removal through the volatilization process during secondary treat-
conditions. In the case of sludge, the solid-water distribution coefficient ment is negligible. Volatilization of the contaminants is controlled by
(Kd), KOW, and the acid dissociation constant (pKa) of the ECs determine Henry's law constant (KH). The KH value in the range of 10−2–
their sorption trend. Kd is the ratio of contaminant concentration in the 10−3 atm m3/mol signifies high volatilization potential (Stenstrom
sludge to the concentration in water, as shown in Eq. (2). et al., 1989). The typical KH values (<10−7) of selected ECs presented
in Table 3 indicate insignificant volatilization of ECs during secondary
C sol wastewater treatment.
Kd ¼ ð2Þ
C aq C sp Secondary biological treatment technologies are most widely
adopted for ECs removal across the globe. Activated sludge
where Csol is the concentration of contaminant on solid phase (sorbed processes (ASP) are the most commonly practiced secondary biological
concentration) (μg/L); Caq is dissolved concentration of the contaminant processes in conventional WWTPs. Other high-rate secondary biological
(μg/L); and, Csp is the concentration of suspended particulates in the processes include constructed wetland, membrane bioreactors (MBRs),
wastewater (kg/L). For contaminants with a Kd value less than trickling filters, biological aerated filters (BAF), rotating biological
300–500 L/kgMLSS, their sorption into sludge is insignificant (Das contactors, moving bed biological reactor (MBBR), fungal bioreactor,
et al., 2017 Goswami et al., 2018). Typical Kd values of some representa- microalgal bioreactor, oxidation ditches, etc. (Roccaro, 2018 Ahmed
tive ECs are presented in Table 3. As shown in Table 3, other than few et al., 2017). The most commonly employed processes like ASP and
antibiotics, hormones, biocides, and artificial sweetener, the ECs have MBRs with higher EC removal efficiency than other technologies are
a Kd value less than 300–500 L/kgMLSS and hence, minimum sorption discussed briefly in the following sections.
can be expected. For the contaminants with KOW < 2.5, the sorption is
minimum, whereas the hydrophobic contaminants (KOW > 4) have 3.2.1. Activated sludge process
high sorption potential to the sludge. As shown in Table 3, azithromycin, The activated sludge process relies on the capability of the activated
diclofenac, and triclosan can be preferentially removed by sorption onto biomass (present in the sludge) to biodegrade/biotransform the ECs.
sludge. The ECs are also sorbed onto the secondary sludge in a similar manner,
Likewise, pKa values of ECs are critical when charge interactions play as discussed in Section 3.1; therefore, the biodegradation aspect is em-
a role in sorption (Petrie et al., 2015). For example, at the pH above pKa phasized in this section. Biodegradation is the breakdown of complex
the phenolic hydroxyl group of hormones dissociates, resulting in a neg- ECs into simpler ones through diversified enzymatic reactions like hy-
atively charged compound, and thereby hindering the sorption of the droxylation, carboxylation, glycosylation, hydrogenation, ring cleavage,
ECs via charge repulsion (Schäfer et al., 2011 Luo et al., 2014). Moreover, etc. by the microorganisms (Xiong et al., 2018). The oxidation of carba-
the sorption of ECs is dependent on the operational conditions of mazepine, hydroxylation and carboxylation of ibuprofen are illustrated
WWTPs such as temperature, hydraulic retention time (HRT), solid re- in Fig. 6. In this treatment process, the ECs are biodegraded to variable
tention time (SRT), etc., since the Kd values are governed by these pa- degrees ranging from complete mineralization (conversion to water
rameters (Tran et al., 2018). For instance, an increase in Kd values was and carbon dioxide) to incomplete degradation resulting in transformed
witnessed for ethinylestradiol and quinolone when the temperature byproducts. For instances, methoxy-triclosan can be biodegraded up to
was reduced, indicating the inverse relation of temperature and sorp- 81% in ASP; however, it is transformed to a lesser degree (56.5%)
tion potential of theses ECs (Norvill et al., 2016). Good removal efficien- through the conversion into a relatively recalcitrant variant, 2,4-dichlo-
cies up to 40% of fragrances (galaxolide and tonalide), 43% of EDCs rophenol when it is exposed to laccase enzyme during ASP (Fig. 6d)
(Bisphenol A), and 28% of hormones (diclofenac and estriol) are re- (Samaras et al., 2013 Xiong et al., 2018).
ported (Carballa et al., 2004 Stasinakis et al., 2013 Behera et al., 2011). Biodegradation of ECs mainly occurs via metabolism and co-
Nevertheless, primary treatment employing aerated grit chamber metabolism (Tran et al., 2018). In metabolism, the microorganisms
could cause a significant increase in phenolic compounds (bisphenol A use the ECs as substrates for cell proliferation and enzyme synthesis
and nonylphenol) due to aeration induced detachment of these com- for carrying out metabolic activities. However, due to lower EC concen-
pounds from the grits (Nie et al., 2012). trations, the generated energy through its degradation may not be suf-
It is important to note that sorption is a phase changing technology ficient to meet the microbial need; in addition, some ECs inhibit
where the ECs move from the liquid phase (wastewater) to the solid microbial growth due to their toxic nature. In these cases, co-
phase (sludge); hence it can only provide temporary risk reduction. metabolism happens where microorganisms rely on a primary carbon
These approaches require further investigations as the ECs removal source to maintain the growth and enzyme synthesis for the EC degra-
mechanisms are still unclear if sorption is followed by degradation or dation (Ahmed et al., 2017). The co-metabolic pathway of ECs biodegra-
vice versa. On one hand, sorption to biosolids may be a preliminary dation in wastewater treatment processes are of common
step to biodegradation; on the other hand, ECs may subsequently de- manifestations than that of metabolism. For example, in nitrifying mi-
sorb upon reaching adsorption equilibrium and return to the liquid croorganisms, the ammonia monooxygenase enzyme catalyzes the co-
phase (Rodriguez-Narvaez et al., 2017). The persistent ECs in sludge metabolic degradation of ECs like ibuprofen, ethinylestradiol, etc.,
can further leach out during sludge treatment and/or disposal, trigger- along with ammonia elimination (Alvarino et al., 2018).
ing a significant challenge, thereby necessitating a careful sludge dis- Biodegradation of ECs depends on the properties of the ECs
posal strategy. Therefore, sorption-based systems can be integrated (e.g., structural complexity, bioavailability, functional groups), sludge
with other treatment technologies for better results. properties (sludge age, biomass activity), and operating conditions
(redox potential, SRT, HRT). For example, linear short chain, unsatu-
3.2. Effect of secondary treatment technologies on ECs removal rated aliphatic compounds with electron donating functional groups
are easily biodegradable as compared to their counterparts, branched
The main mechanisms of ECs removal during secondary treatment chain, saturated polycyclic compounds with electron withdrawing
technologies are biodegradation/biotransformation and sorption, functional groups (Luo et al., 2014). Long SRT enables the development
10 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990

Table 3
Concentration, properties, and removal of selected ECs in WWTPs.

EC types Kd (L/kgMLSS) Kbio Log KOW pKa KH (atm WWTP effluent concentration Sludge concentration (ng/g dry Removal
(L/gMLSS-d) m3/mol) (ng/L) weight) efficiency (%)

Antibiotics
Azithromycin 35.5–2156 <0.13–1.5 4.02 8.74 5.3 × 10−29 175 <MDL-666 <0–99
Ciprofloxacin 19,952.6–38,900 0.025–0.55 0.28 6.09 5.09 × 10−19 96.3 1400–4800 <0–100
Clarithromycin 386–1200 0.034–2.050 3.16 8.99 1.73 × 10−29 276 <MDL-537 <0–99
Erythromycin 74–309 0.125–6 2.37 12.44 1.46 × 10−29 42 6–79 <26.6–77.7
Trimethoprim 119–427 0.05–5.04 1.26 17.33 2.39 × 10−14 100 <MDL-13 <0–97
NSAIDs
Codeine 13–15 4.2–5.4 1.2 13.78 7.58 × 10−14 70.6 <MDL-79 <0–98
Diclofenac 1.9–321 0.02–8 4.98 4 4.73 × 10−12 647 <MDL-133 <0–98
Ibuprofen 6–102.8 3.24–38.7 3.5 4.85 1.5 × 10−7 394 <MDL-3988 <0–99.8
Ketoprofen 16–226 0.24–3.36 3.12 4.45 2.12 × 10−11 86 <MDL-58.4 51.5–91.9
Naproxen 10- < 30 0.2–9 3.29 4.19 3.39 × 10−10 462 <MDL-1022 <0–99.3
Lipid regulators
Clofibric acid 7–87.5 0.03–1 2.57 −4.9 2.19 × 10−8 5.3 <MDL 27.7–71.8
Bezafibrate 87 0.64–4.5 3.97 3.83 NR 139 17–64 48.4–95.8
Gemfibrozil 19.3–45 1.01–9.6 3.4 4.42 NR 137.7 <MDL-1192 0–100
Hormones
Estrone <100–645 2–200 3.13 10.33 3.8 × 10−10 15 <MDL-17.5 0–100
Ethinylestradiol 330–750 0.02–20 3.63 10.33 7.94 × 10−12 2 <MDL-17.5 33–100
Beta-blockers
Atenolol 5.9–95 0.432–5.28 0.16 9.6 1.37 × 10−18 843 <MDL-86 <0–96
Metoprolol 31.3–137.8 0.01–4.32 1.88 14.09 1.4 × 10−13 166 <MDL-226 <0–58.7
Anticonvulsants
Carbamazepine 8–314 0.005–0.389 2.1 15.96 1.08 × 10−10 482 <MDL-50 0–83
X-ray contrast media
−28
Iopromide 14 0.072–2.5 −2.05 NR 1 × 10 876 76–84 31–90
Iopamidol <10 <1.01–2.664 1.62 4.15 1.14 × 10−25 377 NR <0–53.4
Insect repellent
DEET <30–100 0.24–5.76 2.8 NR 2.08 × 10−08 678.1 2–6 27–100
Biocides
Triclosan 1905–9550 0.025–0.55 5.53 7.9 4.99 × 10−9 74.8 354–15,600 <0–100
Miconazole NR NR 0.0008 5.86 NR 0.2 <MDL-2609 <0–99
EDC
Bisphenol A 314–505 0. 24–16.56 3.32 9.6 1 × 10−11 331 <MDL-4700 32–100
Psychoactive drug
Caffeine <30–140 0.48–156.24 −0.07 10.4 1.9 × 10−19 191.1 <MDL-805 84–100
Artificial sweeteners
Sucralose 193–365 0.018–0.05 −1 4.2 NR 4600 <MDL-1980 <0–35.2
Acesulfame 5.1–765 0.173–0.556 −1.33 5.67 NR 22,500 <MDL-1 <0–99

MDL - Method detection limit; NR - Not reported in the literature; Note: The information in this table are mostly summarized from Tran et al. (2018), Das et al. (2017), Tiwari et al. (2017),
Petrie et al. (2015), Luo et al. (2014), Wang and Wang (2016), Yang et al. (2017), http://chem.sis.nlm.nih.gov/chemidplus/, http://www.drugbank.ca/, and https://pubchem.ncbi.nlm.nih.
gov/.

of slow growing microorganisms for the enhanced biodegradation of where dc/dt is the rate of biodegradation of contaminants (μg/L d); Kbio
ECs with very low concentrations, whereas higher HRT facilitates im- is the biodegradation rate constant (L/gMLSS d); Xact is the concentra-
proved degradation of recalcitrant ECs by allowing more reaction tion of active biomass in the wastewater (g/L); and Caq is dissolved con-
times (Norvill et al., 2016). Enhanced biodegradation of triclosan was centration of the contaminant (μg/L). Contaminants with a Kbio value
reported by Stasinakis et al. (2010) at a 20-day SRT as compared to 3 <0.01, 10 > Kbio > 1, and Kbio > 10 are classified as low, moderate and
and 10 days. Similarly, the antibiotic fluoxetiene exhibited less biodeg- highly biodegradable (Tran et al., 2018). Typical Kbio values of some rep-
radation efficiency at shorter HRTs (Fernandez-Fontaina et al., 2012). resentative ECs are presented in Table 3. The reported most significantly
The redox conditions (aerobic, anoxic, anaerobic) are crucial in deter- removed ECs in ASP were NSAIDs like Ibuprofen and naproxen with an
mining the biotransformation pathway of ECs. The aerobic condition fa- average removal efficiency of 91.4% and 75.5%, respectively.
vors biodegradation of a wide range of ECs through dissolved oxygen Despite high EC removal efficiency in ASP, in some cases, the toxicity
induced oxidation, whereas limited biotransformation occurs under of ECs towards microorganisms poses significant challenges, particularly
the anoxic condition. Dorival-García et al. (2013) reported 14–40% bio- during the treatment of antibiotics. Managing the secondary sludge pro-
transformation of quinolone under aerobic conditions, but the recalci- duced during ASP is also another important issue to deal with since
trant nature of the compound was observed under anoxic conditions. there exists a knowledge gap in connection to the presence of ECs in the
However, sulfamithoxazole with an amide functional group was diffi- sludge due to the complex matrix and lack of sensitive analytical tech-
cult to biodegrade under aerobic conditions but was readily niques to monitor ECs in sludge samples (Rodriguez-Narvaez et al.,
biotransformed under anaerobic conditions by reductive reactions due 2017). Identification, quantification, and routine monitoring of reaction
to the presence of the electron-withdrawing sulfonyl group (Alvarino intermediates and transformation products of parent compounds need
et al., 2018). to be explored as transformation products sometimes appear to be
Biodegradability of contaminants can be evaluated based on its bio- more toxic and can revert back to the parent compounds. In addition,
degradation constant (Kbio) as shown in Eq. (3): the issues related to the washout of biomass fraction in effluent resulting
in low active biomass concentration and relatively short SRT need to be
taken care of for further enhancement of the performance efficiency.
dc Therefore, the combination of ASP with other treatment technologies
¼ K bio X act C aq ð3Þ
dt might result in further improvisation of ECs removal efficiencies.
 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990 11

Fig. 6. Microbial biotransformation of ECs (a) oxidation of carabamazepine, (b) hydroxylation of ibuprofen, (c) carboxylation of ibuprofen, and (d) enzymatic biodegradation of methoxy-
triclosan.

3.2.2. Removal of ECs in membrane bioreactors Kwak et al., 2020). Higher SRT promotes improved biodiversity of the
Based on the membrane features (pore size, hydrophobicity) used, microorganisms in MBRs. Membrane retention of biomass facilitates ad-
pressure membrane filtration can be classified as microfiltration (MF aptation/acclimatization of slow growing microbes to the toxic ECs, and
with a pore size = 0.1–1 μm and operating pressure = 5–10 bar), ultra- a decrease or increase of HRT without disturbing SRT helps in better
filtration (UF with a pore size = 0.01–0.1 μm and operating pressure = control of operating conditions as per the targeted ECs. For example, a
5–10 bar), nanofiltration (NF with a pore size = 0.001–0.01 μm and op- higher HRT can be opted for providing more reaction time to a recalci-
erating pressure = 50 bar), and reverse osmosis (RO with a pore size = trant EC whereas maintaining a lower HRT can be beneficial for higher
0.000–0.001 μm and operating pressure = 70–150 bar). Forward osmo- loading of ECs with very low concentrations (Das et al., 2017 Lee et al.,
sis (FO), like RO, uses a semi-permeable membrane and osmotic pres- 2019 Norvill et al., 2016).
sure gradient for the filtration process (Rodriguez-Narvaez et al., 2017 The removal of ECs in MBRs depends on membrane characteristics
Barbosa et al., 2016). Membrane filtration uses hydrostatic pressure to (surface roughness, surface charge, hydrophobicity, and membrane ma-
remove contaminants and allow water and low molecular weight sol- terial), physico-chemical properties of ECs (size, concentration, func-
utes to pass through the membranes as permeate. tional group, charge, polarity) and operating conditions (SRT, pH,
Membrane bioreactors that combine the mechanisms of biological temperature, and redox condition). The main mechanisms for ECs re-
degradation with membrane separation are widely used for the removal moval in MBRs include size exclusion, adsorption onto membrane sur-
of ECs from wastewater in recent times. The MBRs emerged as an alter- face via electrostatic interaction, sorption onto the biofilm layer/
native treatment technology to overcome the limitations of ASP are suc- fouling layer developed on the membrane surface followed by biodeg-
cessful in removing a wide range of ECs that otherwise are difficult to radation, and hydrophobic interaction with the membrane (Fig. 7)
remove in ASP and other secondary treatment technologies (Ahmed (Das et al., 2017 Goswami et al., 2018). Nonpolar ECs are removed
et al., 2017). The higher EC removal efficiency of MBRs is attributed to mostly via size exclusion, adsorption onto membrane surface or onto
a number of distinct features like longer SRT (15–80 days against the biofilm layer (mostly ECs with a size smaller than membrane
7–20 days in ASP), membrane detainment mediated higher biomass pore), whereas biodegradation is the dominant mechanism for polar
concentration, and more significantly separation between SRT and ECs and adsorption is minimal (Goswami et al., 2018). Also, polar and
HRT with membrane retention of biomass/sludge (Barbosa et al., 2016 hydrophilic ECs like estrone, ketoprofe are efficiently removed by UF-
12 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990

Fig. 7. Overall mechanisms of ECs removal in membrane-associated processes.

MBRs as compared to non-polar hydrophilic ECs like phthalate discharge water for reuse purposes. Therefore the advanced treatment
(Rodriguez-Narvaez et al., 2017). Higher removal for diclofenac re- techniques supplement the secondary treatment technologies by re-
ported in a UF-MBR than that of MF-MBR was attributed to its retention moving the persistent ECs that escape the secondary treatment step ei-
by the fouling layer (Alvarino et al., 2018). ECs removal via size exclu- ther due to recalcitrant nature or toxic to the microorganisms (Ahmed
sion can only be achieved significantly by only NF and RO membranes et al., 2017; Wang and Wang, 2016). The main mechanisms for EC re-
(Schäfer et al., 2011). Similarly, lipophilic ECs like fragrances could moval during tertiary treatment are oxidation (that can further miner-
only be retained by hydrophobic membranes like polyethersulfone alize the ECs and their by-products to CO2, H2O, and simple inorganic
membranes. Bisphenol A removal was reported 75% in polysulfone ions) and activated carbon (AC)-based sorption of a wide range of ECs
made UF-MBR, whereas polyvinylidene-made UF-MBR exhibited 98% from secondary wastewater (de Oliveira et al., 2019 Alvarino et al.,
removal efficiency due to efficient membrane material (Rodriguez- 2018). Oxidation processes, like ozonation, UV treatment, chlorination,
Narvaez et al., 2017). Very high removal efficiency of ethinylestradiol photocatalysis, etc., are used for oxidizing ECs (Yang et al., 2017). Like-
(90%), sulfamethoxazole (99.1%), acetaminophen (99.9%) were re- wise, a range of commercially available adsorbents, such as AC, biochar,
ported in pilot-scale MBRs (de Gusseme et al., 2009 Snyder et al., carbon nanotubes, clay minerals, etc., are used for adsorption of ECs
2007). In general, MBRs exhibited better removal efficiency of ECs (Rodriguez-Narvaez et al., 2017). Out of the mentioned options, ozona-
than that of ASP. For instance, the removal efficiency of ECs like tion and AC treatment are found to be economically feasible and imple-
diclofenac, sulfamethoxazole, and clofibric acid was 87.4%, 99.1%, and mented for the WWTP upgrade in Switzerland (Eggen et al., 2014; Rizzo
71.8% in MBRs against the respective values of 50%, 75% and 27% in et al., 2019). Therefore, ozonation and AC treatment are discussed
ASP (Tiwari et al., 2017). briefly in the following two subsections.
One of the major disadvantages of MBR application is that it only fa-
cilitates a separation process where the ECs only change the phase but
not really removed from the environment. The treatment process pro- 3.3.1. Ozonation
duces a dilute phase in the form of permeate and a ECs concentrated Ozonation is a chemical oxidation process that employs ozone (O3)
phase as the rejected effluent. The concentrated phase requires further gas for the oxidation of ECs. It is one of the most promising techniques
treatment before disposed-off. Different approaches are under investi- to considerably reduce the ECs load in WWTPs (Hollender et al.,
gation to provide a sustainable alternative to treat membrane concen- 2009). Ozone can directly react with ECs or can indirectly react via a sec-
trates. One such development is the sequential coupling of ASP with ondary oxidant, hydroxyl radicals (HO•) that are formed due to a side
membrane filtration that achieved very high ECs removal efficiency, reaction of ozone with a specific group of effluent organic matter
where the membrane rejected ECs were removed by the microorgan- (EfOM) like phenols or amines (Rizzo et al., 2019). Improved HO• gen-
isms in the activated sludge (Yang et al., 2011). Another such approach eration through ozone decomposition can be achieved by combining
is the integration of membrane technology with bioelectrochemical sys- O3 with H2O2 and UV (de Oliveira et al., 2019). Ozone is selective in na-
tems (BES), otherwise called as electrochemical membrane bioreactors ture that preferably attacks electron-rich ECs like sulfamethoxazoles,
(EMBR). Combining the mechanisms of membrane filtration, biodegra- and ECs with deprotonated amine groups like trimethoprim mainly at
dation, and bioelectrogenesis (electricity generation by the microorgan- low pH, whereas HO• are fast in action, non-selective in nature, and
isms), EMBRs have been claimed to have higher ECs removal efficiency thus, can attack a wide range of ECs including those resistant to ozone
as compared to MBRs and ASPs with reduced energy consumptions at relatively high pH (Rizzo et al., 2019 Gogoi et al., 2018 Barbosa
(Asif et al., 2020). However, most of these advanced technologies are et al., 2016). Sui et al. (2010) reported a very high removal efficiency
in the laboratory or pilot scales that necessitate further scale-up to (>95%) of diclofenac, carbamazepine, sulpiride, indomethacin, and tri-
filed scale. Moreover, certain limitations of MBRs like membrane foul- methoprim at an ozone dose of 5 mg/L.
ing, high energy demand, and expensive membrane materials need to Based on the removal efficiencies of different ECs at a specific ozone
be addressed for further extensive applications at full scale. dose in the range of 0.4–0.6 g O3/g dissolved organic carbon, the ECs are
categorized into three groups by Rizzo et al. (2019) as presented in
Table 4. The ECs belonging to group A are electron rich compounds,
3.3. Effect of tertiary treatment technologies on ECs removal with a high removal rate due to their high reaction rate with ozone.
On the other hand, ECs in group B are relatively less removed due to
The tertiary or advanced treatment technologies are usually their lower reaction rate with ozone as compared to group A. Similarly,
employed in WWTPs as polishing techniques to produce high quality ECs of group C are ozone resistance, but their reactivity is influenced by
 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990 13

Table 4
Grouping of ECs based on their reactivity to ozone.

Group ECs Degree of Rate Removal

reaction constant, KO3 efficiency
with ozone (M−1 s−1) (%)

A Ciprofloxacin, Carbamazepine, Azithromycin, Clarithromycin, Bisphenol-A, Diclofenac, Sulfamethoxazole, Erythromycin, High >103 >80
Metoprolol, Ethinylestradiol
2 3
B Benzotriazole, Bezafibrate, Methylenbenzotriazole Medium 10 –10 50–80
C Acesulfame, Primidone, Iopromide Low <102 <50

from municipal wastewater treated through ASP (Siegrist et al., 2018).

their reaction with HO• (Rizzo et al., 2019). Ozonation being one of the PAC addition directly in the activated sludge tank or secondary post
most successful techniques, has exhibited removal efficiency as high as treatment systems like a tertiary filter is a major application of PAC in
90–100% of almost all types of ECs. the full-scale WWTPs (Altmann et al., 2014). Similarly, GAC can be filled
An important issue with ozonization is the formation of oxidation into existing sand filters or as a replacement for the upper layer of a ter-
by-products. Mechanisms of ozonation are dependent on pH, tempera- tiary dual media filter in the WWTPs (Grover et al., 2011). The high re-
ture, and ozone doses that interferes with the degradation of ECs (de moval efficiency of selected ECs up to 86% was achieved by Kovalova
Oliveira et al., 2019). When the applied ozone doses are insufficient, it et al. (2013) from an MBR-treated hospital effluent by using a PAC reac-
will result in the formation of transformation products or oxidation tor. Similarly, Grover et al. (2011) reported higher removal efficiency
by-products instead of complete mineralization. At times, a temporary (84–99%) of selected ECs like diclofenac in a full scale GAC plant treating
increase in toxicity after ozonation is attributed to the formation of WWTPs effluent. The removal efficiencies of selected ECs by PAC and
toxic oxidation by-products. The toxicity can further be reduced by a GAC in full scale applications are summarized in Table 5. AC treatments
subsequent biological treatment step after ozonation (Knopp et al., exhibit significant EC removal efficiency and appear as an attractive
2016). Ozonation in combination with biological process implemented method for upgrading WWTPs.
at full scale at UWWTPs in Switzerland is found to be one of the most Compared to ozonation, the AC-mediated adsorption of ECs offers the
efficient approach for the removal of ECs from secondary urban waste- advantage of no by-product formation and lower energy consumption at
water (McArdell, 2015). However, one constraint with ozonation- the WWTPs (Knopp et al., 2016). However, the production of AC requires
combined biological systems is the lack of comprehensive economic a high primary energy demand. Thus, the sustainability of the production
studies that could present this combination as a cost competitive tech- of AC is a significant issue. Small scale kilns requiring high energy inputs
nology (Oller et al., 2011). Moreover, the limitations like high energy due to low efficiency are mostly engaged for AC production; therefore,
consumption, expensiveness of the method due to the short lifetime the scaling-up is another significant issue (Rodriguez-Narvaez et al.,
of ozone, and interference from HO• scavengers in wastewater need to 2017). Identifying efficient and cleaner production of AC and assessing
be considered for further improvisation of ECs removal efficiency. the carbon footprint associated with the production process is essential
to ensure its large scale production. Furthermore, the exhausted adsor-
3.3.2. Activated carbon adsorption bents saturated with ECs are the key challenge of this process that de-
Adsorption also has a phase changing mechanism in which the con- mands adequate treatment and disposal. So, AC adsorption, in
taminants (adsorbates) move from the aqueous phase to the solid combination with other treatments like ultrafiltration and coagulation,
phase (adsorbent) and has been widely explored for the removal of ECs has been proposed for enhanced ECs removal (Acero et al., 2012). How-
(Rodriguez-Narvaez et al., 2017). AC is the most extensively used adsor- ever, the lack of understanding of the full-scale feasibility of the proposed
bent for a broad spectrum ECs adsorption because of its high porosity, processes continues to be a key constraint in the practical application of
large specific surface area and, the high degree of surface interactions these research findings. Full scale applications of GAC and PAC are well
(Rizzo et al., 2019). AC is classified as powder activated carbon (PAC) documented, but more studies are needed considering ACs from different
and granular activated carbon (GAC) based on the particle size and as sources and prepared under different environmental conditions by
macroporous (≥50 nm), mesoporous (2–50 nm), and microporous (2 different, environmentally-friendly technologies for their wider
− > 0.8 nm) based on the pore size. Both PAC and GAC can effectively re- implementations in full scales (Thompson et al., 2016).
move ECs from wastewater, and mesoporous AC was found to be the The overall removal efficiencies of selected ECs in WWTPs are pre-
most suitable for ECs removal due to reduced interference from the or- sented in Fig. 8. The removal efficiencies for the ECs varied widely
ganic materials for the adsorption active sites (Budimirović et al., 2017). from 0 to 100%, depending on the ECs properties and operating condi-
The adsorption efficiency depends on the properties of ECs (molecu- tions. ECs, even in the same class, are removed to significantly different
lar size, polarity, functional group, KOW, Kd, pKa), AC (particle size, sur- degrees. Out of 27 ECs presented in Fig. 8, except erythromycin, clofibric
face area, pore diameter, mineral content) and environmental acid, metoprolol, iopamidol, and sucralose, more than 90% of the re-
conditions (pH, temperature, wastewater type) as discussed elaborately maining ECs are removed in the WWTPs. Thus, WWTPs have been
in previous sections (Luo et al., 2014). The source of the raw material for proved to be effective in eliminating most of the commonly studied
AC is also an important factor that determines ECs removal rates. For ex- ECs by employing primary, secondary, and tertiary treatment technolo-
ample, diclofenac removal was >90% using GAC, whereas poor removal gies, as discussed earlier. The detailed removal efficiency data are com-
was observed using Filtrasorb 400; the differences in efficiency is attrib- piled in Table 3. It is noteworthy to mention that the concentration of
uted to the carbon structure of the raw material (Grover et al., 2011 few ECs was found to be higher in the treated influent than that of the
Sotelo et al., 2012). The wastewater quality and the operational condi- influent. The observed negative removal efficiency has already been
tions of the specific WWTPs also influence ECs removal efficiency. For discussed in previous sections. Therefore, based on the varied removal
instance, the presence of more organic content in the wastewater inter- rates of different ECs in WWTPs, it is not easy to draw a generalized con-
feres in ECs removal efficiency by competing for adsorption active sites clusion on the persistency of different ECs in WWTPs.
on AC. Similarly, the WWTP configuration determines the wastewater
quality based on seasonal variations (Rizzo et al., 2019). However, in 4. Conclusions and future prospective
spite of the discussed variable factors, ECs removal is highly related to
the applied AC dosage. For example, about 1.5–3 g PAC per gram of or- This review provides a brief overview of the classification of ECs,
ganic content present in wastewater is recommended for ECs removal their sources of origin, environmental occurrences, pathways of
14 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990

Table 5
Removal of selected ECs by PAC and GAC adsorption in full scale applications.

Adsorbent Dosage (mg/L) ECs Initial concentration (ng/L) Removal efficiency (%) References

PAC 50 Bezafibrate 1300 90 Altmann et al. (2014)

20–60 17-Alphaethylestradiol 0.24 ± 0.07 83.3 Sun et al. (2017)
20–60 17-Beta estradiol 4.68 ± 0.89 99.9
8–23 Diclofenac NR 96–98 Kovalova et al. (2013)
8–23 Propranolol NR 91–94
15 Sulfamethoxazole NR 58 Boehler et al. (2012)
15 Clarithromycin NR 88
15 Carbamazepine NR 92
15 Iopromide NR 70
15 Mecoprop NR 65
20–60 Bisphenol A 12.60 ± 2.02 53
GAC NR Sulfamethoxazole NR 90 Altmann et al. (2014)
NR Erythromycin 300 ± 200 99.9 Knopp et al. (2016)
NR Ciproflaxacin 130 82.3 Yang et al. (2011)
NR 17-Alphaethylestradiol <20 50
NR Diclofenac NR >98 Grover et al. (2011)
NR 17-Beta estradiol 2 >43
NR Carbamazepine 66 23
NR Metoprolol NR 95 Kårelid et al. (2017)
NR Iopromide NR >80 Reungoat et al. (2011)
29 g/70.6 mL bed volume Bisphenol A NR 66 Hernández-Leal et al. (2011)
29 g/70.6 mL bed volume Nonylphenol NR 84
29 g/70.6 mL bed volume Triclosan NR 95
29 g/70.6 mL bed volume Galaxolide NR 79

migration to different environmental compartments, and different ozonation, the generation of toxic oxidation by-products and their oc-
treatment technologies for the removal of ECs in WWTPs. Nevertheless, currence in both dissolved and particulate phases necessitates a biolog-
from the review of the available treatment technologies, it can be in- ical post-treatment to cope with the issue.
ferred that achieving significant ECs removal using a single treatment Additional generalized conclusions are as follows: The fate and dis-
technology is challenging. The use of integrated systems where the lim- tribution of ECs can be approximately estimated based on physicochem-
itations of the individual treatment technologies can be bridged appears ical properties like log KOW (>4, maximum sorption potential) and Kd
as promising alternatives for efficient ECs removal from the environ- (<300–500 L/kgMLSS, sorption into sludge is insignificant). Based on
ment. However, the majority of the alternative treatment technologies RQ values the risk levels of ECs are categorized as negligible risk
investigated/proposed, are in lab-scales, lacking the full-scale WWTPs (RQ < 0.01), low risk (0.01 > RQ < 0.1), medium risk (0.1 > RQ < 1),
implementation feasibility information. Though most of the commonly and high risk (RQ > 1). Activated sludge based biological treatment pro-
investigated ECs were substantially reduced in WWTPs effluent, some cesses are commonly unable to remove persistent ECs completely; how-
persisted; others were found to be more toxic than the parent com- ever, efficiency can be improved through improvisation of operating
pounds and few exhibited negative removal efficiency. During conditions (long SRT, high HRT). Biodegradation potential of ECs can

120
WWTPs

100
Maximum removal efficiencies of ECs in

80

60
(%)

40

20

Emerging Contaminants (ECs)

Fig. 8. Maximum removal efficiencies of selected ECs in WWTPs. Percentage errors of the data are presented by error bars. (Detailed data complied in Table 3).
 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990 15

be predicted from Kbio values (e.g., <0.01 = low biodegradation and References
>10 = high biodegradation). MBRs are found to be very effective for
Acero, J.L., Benitez, F.J., Real, F.J., Teva, F., 2012. Coupling of adsorption, coagulation, and
the removal of many persistent ECs through highly-concentrated active ultrafiltration processes for the removal of emerging contaminants in a secondary ef-
biomass retention. With the reported maximum ECs removal efficiency, fluent. Chem. Eng. J. 210, 1–8.
so far, tertiary treatment technologies are considered as the most suit- Ahmed, M.B., Zhou, J.L., Ngo, H.H., Guo, W., Thomaidis, N.S., Xu, J., 2017. Progress in the
biological and chemical treatment technologies for emerging contaminant removal
able alternatives for ECs treatment, but complete ECs removal is yet to from wastewater: a critical review. J. Hazard. Mater. 323, 274–298.
be achieved. Optimization of WWTPs with tertiary and combined treat- Altmann, J., Ruhl, A.S., Zietzschmann, F., Jekel, M., 2014. Direct comparison of ozonation
ment to create an absolute barrier to ECs emission remains a task of high and adsorption onto powdered activated carbon for micropollutant removal in ad-
vanced wastewater treatment. Water Res. 55, 185–193.
priority. Therefore, further advancements in the treatment technologies
Alvarino, T., Suarez, S., Lema, J., Omil, F., 2018. Understanding the sorption and biotrans-
will unquestionably be necessary for the complete removal of ECs in formation of organic micropollutants in innovative biological wastewater treatment
WWTPs. technologies. Sci. Total Environ. 615, 297–306.
Despite progressive developments in ECs treatment technologies, Archer, E., Petrie, B., Kasprzyk-Hordern, B., Wolfaardt, G.M., 2017. The fate of pharmaceu-
ticals and personal care products (PPCPs), endocrine disrupting contaminants
significant limitations still exist, necessitating future research for the re- (EDCs), metabolites and illicit drugs in a WWTW and environmental waters.
alization of a holistic ECs removal technology. The prevalent challenges Chemosphere 174, 437–446.
and related research directions are as follows: Asif, M.B., Maqbool, T., Zhang, Z., 2020. Electrochemical membrane bioreactors: state-of-
the-art and future prospects. Sci. Total Environ. 741, 140233.
1. Owing to the detection and treatment difficulties of ECs, concentra- Barbosa, M.O., Moreira, N.F., Ribeiro, A.R., Pereira, M.F., Silva, A.M., 2016. Occurrence and
removal of organic micropollutants: an overview of the watch list of EU Decision
tion reduction at source needs to be emphasized through legislation, 2015/495. Water Res. 94, 257–279.
imposing restricted environmental release of the compounds, and Behera, S.K., Kim, H.W., Oh, J.E., Park, H.S., 2011. Occurrence and removal of antibiotics,
public awareness. hormones and several other pharmaceuticals in wastewater treatment plants of the
largest industrial city of Korea. Sci. Total Environ. 409 (20), 4351–4360.
2. Transform products of ECs are not generally monitored due to the
Bermúdez-Couso, A., Fernández-Calviño, D., Álvarez-Enjo, M.A., Simal-Gándara, J., Nóvoa-
lack of knowledge of their persistency and toxicity. The development Muñoz, J.C., Arias-Estévez, M., 2013. Pollution of surface waters by metalaxyl and ni-
of new protocols should be focused on the extraction of ECs or their trate from non-point sources. Sci. Total Environ. 461, 282–289.
Bhandari, A., Surampalli, R., Adams, C.D., Champagne, P., Ong, S.-K., Tyagi, R.D., Zhang, T.C.,
transformation products from complex environmental matrices like
2009. Contaminants of Emerging Environmental Concern. ASCE, Reston, Virginia,
sludge and on their quantification/identification. p. 2009.
3. During biodegradation, normally the overall effects of operating con- Boehler, M., Zwickenpflug, B., Hollender, J., Ternes, T., Joss, A., Siegrist, H., 2012. Removal
ditions (SRT, HRT) are investigated, instead of examining the individ- of micropollutants in municipal wastewater treatment plants by powder-activated
carbon. Water Sci. Technol. 66 (10), 2115–2121.
ual or combined effects of these experimental parameters. Therefore, Budimirović, D., Veličković, Z.S., Djokić, V.R., Milosavljević, M., Markovski, J., Lević, S.,
systemic studies should be undertaken to optimize the parameters Marinković, A.D., 2017. Efficient As (V) removal by α-FeOOH and α-FeOOH/α-
for the maximization of removal efficiency of ECs. MnO2 embedded PEG-6-arm functionalized multiwall carbon nanotubes. Chem.
Eng. Res. Des. 119, 75–86.
4. Membrane fouling is a prevalent issue of MBRs, restricting their ap- Carballa, M., Omil, F., Lema, J.M., Llompart, M., García-Jares, C., Rodríguez, I., Gomez, M.,
plications to some extent. However, ECs can be retained and subse- Ternes, T., 2004. Behavior of pharmaceuticals, cosmetics and hormones in a sewage
quently removed by interacting with the fouling layer. Thus, the treatment plant. Water Res. 38 (12), 2918–2926.
Carson, R., 2002. Silent Spring. Houghton Mifflin Harcourt.
positive and negative contributions of fouling mechanisms need to
CE (Commission European), 2016. Communication From the Commission to the
be analyzed. European Parliament, the Council, the European Economic and Social Committee
5. During the advanced oxidation process, hydroxyl radicals can either and the Committee of the Regions. A European Agenda for the Collaborative
Economy.
mineralize the ECs or generate transform by products. Therefore,
Cleuvers, M., 2003. Aquatic ecotoxicity of pharmaceuticals including the assessment of
knowledge of formed intermediate and their characterization is es- combination effects. Toxicol. Lett. 142 (3), 185–194.
sential to prevent further possible environmental hazards. Coutu, S., Wyrsch, V., Wynn, H.K., Rossi, L., Barry, D.A., 2013. Temporal dynamics of anti-
6. Despite its significant ECs removal efficiency, AC adsorption provides biotics in wastewater treatment plant influent. Sci. Total Environ. 458, 20–26.
Das, S., Ray, N.M., Wan, J., Khan, A., Chakraborty, T., Ray, M.B., 2017. Micropollutants in
a partial solution as it removes the ECs from one phase and concen- wastewater: fate and removal processes. Physico-Chemical Wastewater Treatment
trates in another. Therefore, ECs saturated AC needs further research and Resource Recovery 75–117.
attention for subsequent treatment for reusability or proper disposal. Daughton, C.G., 2010. Pharmaceutical ingredients in drinking water: overview of occur-
rence and significance of human exposure. Contaminants of Emerging Concern in
7. Metal and non-metallic pillared clays with their enhanced catalytic the Environment: Ecological and Human Health Considerations. American Chemical
and adsorptive properties are finding extensive environmental appli- Society, pp. 9–68.
cations. Exploring the application possibilities of these materials to Díaz-Garduño, B., Pintado-Herrera, M.G., Biel-Maeso, M., Rueda-Márquez, J.J., Lara-Martín,
P.A., Perales, J.A., Manzano, M.A., Garrido-Pérez, C., Martín-Díaz, M.L., 2017. Environ-
remove of ECs will be an essential area for further research.
mental risk assessment of effluents as a whole emerging contaminant: efficiency of
alternative tertiary treatments for wastewater depuration. Water Res. 119, 136–149.
CRediT authorship contribution statement Dorival-García, N., Zafra-Gómez, A., Navalón, A., González-López, J., Hontoria, E., Vílchez,
J.L., 2013. Removal and degradation characteristics of quinolone antibiotics in
laboratory-scale activated sludge reactors under aerobic, nitrifying and anoxic condi-
Prangya R. Rout: Conceptualization, Original draft preparation. Tian tions. J. Environ. Manag. 120, 75–83.
C. Zhang: Reviewing and Editing, final approval of the version to be sub- Dougherty, J.A., Swarzenski, P.W., Dinicola, R.S., Reinhard, M., 2010. Occurrence of herbi-
mitted. Puspendu Bhunia: Reviewing and Editing. Rao Y. Surampalli: cides and pharmaceutical and personal care products in surface water and ground-
water around Liberty Bay, Puget Sound, Washington. J. Environ. Qual. 39 (4),
Conceptualization, Supervision, final approval of the version to be 1173–1180.
submitted. Eggen, R.I., Hollender, J., Joss, A., Schärer, M., Stamm, C., 2014. Reducing the discharge of
micropollutants in the aquatic environment: the benefits of upgrading wastewater
treatment plants. Environnemental Science and Technology 48, 7683–7689.
Declaration of competing interest Fernandez-Fontaina, E., Omil, F., Lema, J.M., Carballa, M., 2012. Influence of nitrifying con-
ditions on the biodegradation and sorption of emerging micropollutants. Water Res.
The authors declare that they have no known competing financial 46 (16), 5434–5444.
Ferrando-Climent, L., Rodriguez-Mozaz, S., Barceló, D., 2014. Incidence of anticancer drugs
interests or personal relationships that could have appeared to influ- in an aquatic urban system: from hospital effluents through urban wastewater to
ence the work reported in this paper. natural environment. Environ. Pollut. 193, 216–223.
Frye, C., Bo, E., Calamandrei, G., Calza, L., Dessì-Fulgheri, F., Fernández, M., Fusani, L., Kah,
O., Kajta, M., Le Page, Y., Patisaul, H.B., 2012. Endocrine disrupters: a review of some
Acknowledgements sources, effects, and mechanisms of actions on behaviour and neuroendocrine sys-
tems. J. Neuroendocrinol. 24 (1), 144–159.
Gogoi, A., Mazumder, P., Tyagi, V.K., Chaminda, G.T., An, A.K., Kumar, M., 2018. Occurrence
This work was supported by Global Institute for Energy, Environ-
and fate of emerging contaminants in water environment: a review. Groundw. Sus-
ment, and Sustainability (GIEES), Kansas, USA. tain. Dev. 6, 169–180.
16 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990

Goswami, L., Kumar, R.V., Borah, S.N., Manikandan, N.A., Pakshirajan, K., Pugazhenthi, G., Kwak, W., Rout, P.R., Lee, E., Bae, J., 2020. Influence of hydraulic retention time and tem-
2018. Membrane bioreactor and integrated membrane bioreactor systems for perature on the performance of an anaerobic ammonium oxidation fluidized bed
micropollutant removal from wastewater: a review. Journal of Water Process Engi- membrane bioreactor for low-strength ammonia wastewater treatment. Chem.
neering 26, 314–328. Eng. J. 386, 123992.
Grandclément, C., Seyssiecq, I., Piram, A., Wong-Wah-Chung, P., Vanot, G., Tiliacos, N., Lee, E., Rout, P.R., Shin, C., Bae, J., 2019. Effects of sodium hypochlorite concentration on
Roche, N., Doumenq, P., 2017. From the conventional biological wastewater treat- the methanogenic activity in an anaerobic fluidized membrane bioreactor. Sci. Total
ment to hybrid processes, the evaluation of organic micropollutant removal: a re- Environ. 678, 85–93.
view. Water Res. 111, 297–317. Luo, Y., Guo, W., Ngo, H.H., Nghiem, L.D., Hai, F.I., Zhang, J., Liang, S., Wang, X.C., 2014. A
Grenni, P., Ancona, V., Caracciolo, A.B., 2018. Ecological effects of antibiotics on natural review on the occurrence of micropollutants in the aquatic environment and their
ecosystems: a review. Microchem. J. 136, 25–39. fate and removal during wastewater treatment. Sci. Total Environ. 473, 619–641.
Gros, M., Petrović, M., Barceló, D., 2007. Wastewater treatment plants as a pathway for Martín, J., Camacho-Muñoz, M.D., Santos, J.L., Aparicio, I., Alonso, E., 2012. Distribution and
aquatic contamination by pharmaceuticals in the Ebro river basin (northeast temporal evolution of pharmaceutically active compounds alongside sewage sludge
Spain). Environmental Toxicology and Chemistry: An International Journal 26 (8), treatment. Risk assessment of sludge application onto soils. J. Environ. Manag. 102,
1553–1562. 18–25.
Gross-Sorokin, M.Y., Roast, S.D., Brighty, G.C., 2006. Assessment of feminization of male McArdell, C., 2015. The first full-scale advanced ozonation plant in the Dübendorf WWTP
fish in English rivers by the Environment Agency of England and Wales. Environ. running; the new Swiss water protection act approved. Norman Bulletin 4, 36–37.
Health Perspect. 114 (Suppl. 1), 147–151. Mohapatra, D.P., Kirpalani, D.M., 2019. Advancement in treatment of wastewater: fate of
Grover, D.P., Zhou, J.L., Frickers, P.E., Readman, J.W., 2011. Improved removal of estrogenic emerging contaminants. Can. J. Chem. Eng. 97 (10), 2621–2631.
and pharmaceutical compounds in sewage effluent by full scale granular activated Nie, Y., Qiang, Z., Zhang, H., Ben, W., 2012. Fate and seasonal variation of endocrine-
carbon: impact on receiving river water. J. Hazard. Mater. 185 (2–3), 1005–1011. disrupting chemicals in a sewage treatment plant with A/A/O process. Sep. Purif.
de Gusseme, B., Pycke, B., Hennebel, T., Marcoen, A., Vlaeminck, S.E., Noppe, H., ... Technol. 84, 9–15.
Verstraete, W., 2009. Biological removal of 17α-ethinylestradiol by a nitrifier enrich- Noguera-Oviedo, K., Aga, D.S., 2016. Lessons learned from more than two decades of re-
ment culture in a membrane bioreactor. Water research 43 (9), 2493–2503. search on emerging contaminants in the environment. J. Hazard. Mater. 316,
Hartmann, J., van Driezum, I., Ohana, D., Lynch, G., Berendsen, B., Wuijts, S., van der Hoek, 242–251.
J.P., de Roda Husman, A.M., 2020. The effective design of sampling campaigns for Norvill, Z.N., Shilton, A., Guieysse, B., 2016. Emerging contaminant degradation and re-
emerging chemical and microbial contaminants in drinking water and its resources moval in algal wastewater treatment ponds: identifying the research gaps.
based on literature mining. Sci. Total Environ. 140546. J. Hazard. Mater. 313, 291–309.
Hernández-Leal, L., Temmink, H., Zeeman, G., Buisman, C.J.N., 2011. Removal of Oaks, J.L., Gilbert, M., Virani, M.Z., Watson, R.T., Meteyer, C.U., Rideout, B.A., Shivaprasad,
micropollutants from aerobically treated grey water via ozone and activated carbon. H.L., Ahmed, S., Chaudhry, M.J.I., Arshad, M., Mahmood, S., 2004. Diclofenac residues
Water Res. 45 (9), 2887–2896. as the cause of vulture population decline in Pakistan. Nature 427 (6975), 630–633.
Hollender, J., Zimmermann, S.G., Koepke, S., Krauss, M., McArdell, C.S., Ort, C., Singer, H.,
Olaitan, J.O., Anyakora, C., Adetifa, I.O., Adepoju-bello, A.A., 2017. A screening for selected
von Gunten, U., Siegrist, H., 2009. Elimination of organic micropollutants in a munic-
human pharmaceuticals in water using SPE-HPLC, Ogun State, Nigeria. African
ipal wastewater treatment plant upgraded with a full-scale post-ozonation followed
J. Pharm. Sci. Pharm. 5, 1–14.
by sand filtration. Environmental Science & Technology 43 (20), 7862–7869.
de Oliveira, M., Frihling, B.E.F., Velasques, J., Magalhães Filho, F.J.C., Cavalheri, P.S., Migliolo,
http://chem.sis.nlm.nih.gov/chemidplus/.
L., 2019. Pharmaceuticals residues and xenobiotics contaminants: occurrence, analyt-
http://www.drugbank.ca/.
ical techniques and sustainable alternatives for wastewater treatment. Sci. Total En-
https://pubchem.ncbi.nlm.nih.gov/. viron. 135568.
Hughes, S.R., Kay, P., Brown, L.E., 2013. Global synthesis and critical evaluation of pharma- Oller, I., Malato, S., Sánchez-Pérez, J., 2011. Combination of advanced oxidation processes
ceutical data sets collected from river systems. Environmental Science & Technology and biological treatments for wastewater decontamination—a review. Sci. Total Envi-
47 (2), 661–677. ron. 409 (20), 4141–4166.
Jones, O.A.H., Voulvoulis, N., Lester, J.N., 2001. Human pharmaceuticals in the aquatic en-
Osorio, V., Imbert-Bouchard, M., Zonja, B., Abad, J.L., Pérez, S., Barceló, D., 2014. Simulta-
vironment a review. Environ. Technol. 22 (12), 1383–1394.
neous determination of diclofenac, its human metabolites and microbial nitration/
Jukosky, J.A., Watzin, M.C., Leiter, J.C., 2008. The effects of environmentally relevant mix- nitrosation transformation products in wastewaters by liquid chromatography/
tures of estrogens on Japanese medaka (Oryzias latipes) reproduction. Aquat. Toxicol. quadrupole-linear ion trap mass spectrometry. J. Chromatogr. A 1347, 63–71.
86 (2), 323–331.
Pal, A., Gin, K.Y.H., Lin, A.Y.C., Reinhard, M., 2010. Impacts of emerging organic contami-
Jungnickel, C., Stock, F., Brandsch, T., Ranke, J., 2008. Risk assessment of biocides in roof nants on freshwater resources: review of recent occurrences, sources, fate and effects.
paint. Environ. Sci. Pollut. Res. 15 (3), 258. Sci. Total Environ. 408 (24), 6062–6069.
Kårelid, V., Larsson, G., Björlenius, B., 2017. Pilot-scale removal of pharmaceuticals in mu-
Paz, A., Tadmor, G., Malchi, T., Blotevogel, J., Borch, T., Polubesova, T., Chefetz, B., 2016. Fate
nicipal wastewater: comparison of granular and powdered activated carbon treat-
of carbamazepine, its metabolites, and lamotrigine in soils irrigated with reclaimed
ment at three wastewater treatment plants. J. Environ. Manag. 193, 491–502.
wastewater: sorption, leaching and plant uptake. Chemosphere 160, 22–29.
Karnjanapiboonwong, A., Suski, J.G., Shah, A.A., Cai, Q., Morse, A.N., Anderson, T.A., 2011.
Peake, B.M., Braund, R., Tong, A.Y., Tremblay, L.A., 2016. Impact of pharmaceuticals on the
Occurrence of PPCPs at a wastewater treatment plant and in soil and groundwater
environment. The Life-Cycle of Pharmaceuticals in the Environment 109–152.
at a land application site. Water Air Soil Pollut. 216 (1–4), 257–273.
Pesqueira, J.F., Pereira, M.F.R., Silva, A., 2020. Environmental impact assessment of ad-
Kasprzyk-Hordern, B., Dinsdale, R.M., Guwy, A.J., 2009. The removal of pharmaceuticals,
vanced urban wastewater treatment technologies for the removal of priority sub-
personal care products, endocrine disruptors and illicit drugs during wastewater
stances and contaminants of emerging concern: a review. J. Clean. Prod. 261, 121078.
treatment and its impact on the quality of receiving waters. Water Res. 43 (2),
363–380. Petrie, B., Barden, R., Kasprzyk-Hordern, B., 2015. A review on emerging contaminants in
wastewaters and the environment: current knowledge, understudied areas and rec-
Kim, M., Guerra, P., Shah, A., Parsa, M., Alaee, M., Smyth, S.A., 2014. Removal of pharma-
ommendations for future monitoring. Water Res. 72, 3–27.
ceuticals and personal care products in a membrane bioreactor wastewater treat-
ment plant. Water Sci. Technol. 69 (11), 2221–2229. Philip, J.M., Aravind, U.K., Aravindakumar, C.T., 2018. Emerging contaminants in Indian
environmental matrices–a review. Chemosphere 190, 307–326.
Kim, K.H., Kabir, E., Jahan, S.A., 2017. Exposure to pesticides and the associated human
health effects. Sci. Total Environ. 575, 525–535. Pruden, A., Pei, R., Storteboom, H., Carlson, K.H., 2006. Antibiotic resistance genes as
Kleywegt, S., Pileggi, V., Yang, P., Hao, C., Zhao, X., Rocks, C., Thach, S., Cheung, P., emerging contaminants: studies in northern Colorado. Environmental Science &
Whitehead, B., 2011. Pharmaceuticals, hormones and bisphenol A in untreated source Technology 40 (23), 7445–7450.
and finished drinking water in Ontario, Canada—occurrence and treatment efficiency. Quinlan, E.L., Nietch, C.T., Blocksom, K., Lazorchak, J.M., Batt, A.L., Griffiths, R., Klemm, D.J.,
Sci. Total Environ. 409 (8), 1481–1488. 2011. Temporal dynamics of periphyton exposed to tetracycline in stream
Knopp, G., Prasse, C., Ternes, T.A., Cornel, P., 2016. Elimination of micropollutants and mesocosms. Environmental Science & Technology 45 (24), 10684–10690.
transformation products from a wastewater treatment plant effluent through pilot Reungoat, J., Escher, B.I., Macova, M., Keller, J., 2011. Biofiltration of wastewater treatment
scale ozonation followed by various activated carbon and biological filters. Water plant effluent: effective removal of pharmaceuticals and personal care products and
Res. 100, 580–592. reduction of toxicity. Water Res. 45 (9), 2751–2762.
Kolpin, D.W., Furlong, E.T., Meyer, M.T., Thurman, E.M., Zaugg, S.D., Barber, L.B., Buxton, Rizzo, L., Malato, S., Antakyali, D., Beretsou, V.G., Đolić, M.B., Gernjak, W., Heath, E.,
H.T., 2002. Pharmaceuticals, hormones, and other organic wastewater contaminants Ivancev-Tumbas, I., Karaolia, P., Ribeiro, A.R.L., Mascolo, G., 2019. Consolidated vs
in US streams, 1999–2000: a national reconnaissance. Environmental Science & Tech- new advanced treatment methods for the removal of contaminants of emerging con-
nology 36 (6), 1202–1211. cern from urban wastewater. Sci. Total Environ. 655, 986–1008.
K’oreje, K.O., Vergeynst, L., Ombaka, D., De Wispelaere, P., Okoth, M., Van Langenhove, H., Roccaro, P., 2018. Treatment processes for municipal wastewater reclamation: the chal-
Demeestere, K., 2016. Occurrence patterns of pharmaceutical residues in wastewater, lenges of emerging contaminants and direct potable reuse. Current Opinion in Envi-
surface water and groundwater of Nairobi and Kisumu city, Kenya. Chemosphere ronmental Science & Health 2, 46–54.
149, 238–244. Rodriguez-Narvaez, O.M., Peralta-Hernandez, J.M., Goonetilleke, A., Bandala, E.R., 2017.
K’oreje, K.O., Okoth, M., Van Langenhove, H., Demeestere, K., 2020. Occurrence and treat- Treatment technologies for emerging contaminants in water: a review. Chem. Eng.
ment of contaminants of emerging concern in the African aquatic environment: liter- J. 323, 361–380.
ature review and a look ahead. J. Environ. Manag. 254, 109752. Rogers, H.R., 1996. Sources, behaviour and fate of organic contaminants during sewage
Kovalova, L., Siegrist, H., Von Gunten, U., Eugster, J., Hagenbuch, M., Wittmer, A., Moser, R., treatment and in sewage sludges. Sci. Total Environ. 185 (1–3), 3–26.
McArdell, C.S., 2013. Elimination of micropollutants during post-treatment of hospital Rout, P.R., Dash, R.R., Bhunia, P., 2016. Development of an integrated system for the treat-
wastewater with powdered activated carbon, ozone, and UV. Environmental Science ment of rural domestic wastewater: emphasis on nutrient removal. RSC Adv. 6 (54),
& Technology 47 (14), 7899–7908. 49236–49249.
 P.R. Rout et al. / Science of the Total Environment 753 (2021) 141990 17

Rout, P.R., Bhunia, P., Dash, R.R., 2017. Response surface optimization of phosphate re- Stenstrom, M.K., Cardinal, L., Libra, J., 1989. Treatment of hazardous substances in waste-
moval from aqueous solution using a natural adsorbent. Trends in Asian Water Envi- water treatment plants. Environ. Prog. 8 (2), 107–112.
ronmental Science and Technology. Springer, Cham, pp. 93–104. Stepien, D.K., Regnery, J., Merz, C., Püttmann, W., 2013. Behavior of organophosphates and
Sakamoto, H., Shoji, S., Kaneko, H., 2007. Leaching characteristics of bisphenol A from hydrophilic ethers during bank filtration and their potential application as organic
epoxy-resin pavement materials. Toxicol. Environ. Chem. 89 (2), 191–203. tracers. A field study from the Oderbruch, Germany. Sci. Total Environ. 458, 150–159.
Samaras, V.G., Stasinakis, A.S., Mamais, D., Thomaidis, N.S., Lekkas, T.D., 2013. Fate of se- Sui, Q., Huang, J., Deng, S., Yu, G., Fan, Q., 2010. Occurrence and removal of pharmaceuti-
lected pharmaceuticals and synthetic endocrine disrupting compounds during cals, caffeine and DEET in wastewater treatment plants of Beijing, China. Water Res.
wastewater treatment and sludge anaerobic digestion. J. Hazard. Mater. 244, 44 (2), 417–426.
259–267. Sun, J., Wang, J., Zhang, R., Wei, D., Long, Q., Huang, Y., Xie, X., Xie, X., Li, A., 2017. Compar-
Santos, J.L., Aparicio, I., Callejón, M., Alonso, E., 2009. Occurrence of pharmaceutically ac- ison of different advanced treatment processes in removing endocrine disruption ef-
tive compounds during 1-year period in wastewaters from four wastewater treat- fects from municipal wastewater secondary effluent. Chemosphere 168, 1–9.
ment plants in Seville (Spain). J. Hazard. Mater. 164 (2–3), 1509–1516. Thompson, K.A., Shimabuku, K.K., Kearns, J.P., Knappe, D.R., Summers, R.S., Cook, S.M.,
Sauvé, S., Desrosiers, M., 2014. A review of what is an emerging contaminant. Chemistry 2016. Environmental comparison of biochar and activated carbon for tertiary waste-
Central Journal 8 (1), 1–7. water treatment. Environmental Science & Technology 50 (20), 11253–11262.
Schäfer, A.I., Akanyeti, I., Semião, A.J., 2011. Micropollutant sorption to membrane poly- Tiwari, B., Sellamuthu, B., Ouarda, Y., Drogui, P., Tyagi, R.D., Buelna, G., 2017. Review on
mers: a review of mechanisms for estrogens. Adv. Colloid Interf. Sci. 164 (1–2), fate and mechanism of removal of pharmaceutical pollutants from wastewater
100–117. using biological approach. Bioresour. Technol. 224, 1–12.
Schlüter-Vorberg, L., Prasse, C., Ternes, T.A., Mückter, H., Coors, A., 2015. Toxification by Tran, N.H., Reinhard, M., Gin, K.Y.H., 2018. Occurrence and fate of emerging contaminants
transformation in conventional and advanced wastewater treatment: the antiviral in municipal wastewater treatment plants from different geographical regions-a re-
drug acyclovir. Environmental Science & Technology Letters 2 (12), 342–346. view. Water Res. 133, 182–207.
Siegrist, H., Joss, A., Boehler, M., McArdell, C.S., Ternes, T., 2018. Organic micropollutant USGS, 2017. Contaminants of Emerging Concern in the Environment. Environmental
control. Advances in Wastewater Treatment. IWA Publishing. Health - Toxic Substances Hydrology Program. U.S. Geological Survey.
Snyder, S.A., Adham, S., Redding, A.M., Cannon, F.S., DeCarolis, J., Oppenheimer, J., Wert, Vulliet, E., Cren-Olivé, C., Grenier-Loustalot, M.F., 2011. Occurrence of pharmaceuticals
E.C., Yoon, Y., 2007. Role of membranes and activated carbon in the removal of endo- and hormones in drinking water treated from surface waters. Environ. Chem. Lett.
crine disruptors and pharmaceuticals. Desalination 202 (1–3), 156–181. 9 (1), 103–114.
Sotelo, J.L., Rodríguez, A., Álvarez, S., García, J., 2012. Removal of caffeine and diclofenac on Wang, J., Wang, S., 2016. Removal of pharmaceuticals and personal care products (PPCPs)
activated carbon in fixed bed column. Chem. Eng. Res. Des. 90 (7), 967–974. from wastewater: a review. J. Environ. Manag. 182, 620–640.
Stackelberg, P.E., Furlong, E.T., Meyer, M.T., Zaugg, S.D., Henderson, A.K., Reissman, D.B., Xiong, J.Q., Kurade, M.B., Jeon, B.H., 2018. Can microalgae remove pharmaceutical con-
2004. Persistence of pharmaceutical compounds and other organic wastewater con- taminants from water? Trends Biotechnol. 36 (1), 30–44.
taminants in a conventional drinking-water-treatment plant. Sci. Total Environ. 329 Yang, X., Flowers, R.C., Weinberg, H.S., Singer, P.C., 2011. Occurrence and removal of phar-
(1–3), 99–113. maceuticals and personal care products (PPCPs) in an advanced wastewater reclama-
Stasinakis, A.S., Kordoutis, C.I., Tsiouma, V.C., Gatidou, G., Thomaidis, N.S., 2010. Removal tion plant. Water Res. 45 (16), 5218–5228.
of selected endocrine disrupters in activated sludge systems: effect of sludge reten- Yang, Y., Ok, Y.S., Kim, K.H., Kwon, E.E., Tsang, Y.F., 2017. Occurrences and removal of
tion time on their sorption and biodegradation. Bioresour. Technol. 101 (7), pharmaceuticals and personal care products (PPCPs) in drinking water and water/
2090–2095. sewage treatment plants: a review. Sci. Total Environ. 596, 303–320.
Stasinakis, A.S., Thomaidis, N.S., Arvaniti, O.S., Asimakopoulos, A.G., Samaras, V.G., Ajibola, Zhou, H., Wu, C., Huang, X., Gao, M., Wen, X., Tsuno, H., Tanaka, H., 2010. Occurrence of
A., Mamais, D., Lekkas, T.D., 2013. Contribution of primary and secondary treatment selected pharmaceuticals and caffeine in sewage treatment plants and receiving riv-
on the removal of benzothiazoles, benzotriazoles, endocrine disruptors, pharmaceu- ers in Beijing, China. Water Environment Research 82 (11), 2239–2248.
ticals and perfluorinated compounds in a sewage treatment plant. Sci. Total Environ.
463, 1067–1075.